Liquid fuel compositions

ABSTRACT

Liquid fuel compositions comprising one or more C 4+  compounds derived from a water-soluble oxygenated hydrocarbon.

The present application claims the benefit of U.S. ProvisionalApplication Ser. No. 61/094,482, filed Sep. 5, 2008 the entiredisclosure of which is hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to liquid fuel compositions comprising acomponent derived from a water-soluble oxygenated hydrocarbon.

BACKGROUND OF THE INVENTION

Significant amount of attention has been placed on developing newtechnologies for providing energy from resources other than fossilfuels. Biomass is a resource that shows promise as a fossil fuelalternative. As opposed to fossil fuel, biomass is also renewable.

One type of biomass is plant biomass. Plant biomass is the most abundantsource of carbohydrate in the world due to the lignocellulosic materialscomposing the cell walls in higher plants. Plant cell walls are dividedinto two sections, primary cell walls and secondary cell walls. Theprimary cell wall provides structure for expanding cells and is composedof three major polysaccharides (cellulose, pectin, and hemicellulose)and one group of glycoproteins. The secondary cell wall, which isproduced after the cell has finished growing, also containspolysaccharides and is strengthened through polymeric lignin covalentlycross-linked to hemicellulose. Hemicellulose and pectin are typicallyfound in abundance, but cellulose is the predominant polysaccharide andthe most abundant source of carbohydrates.

Most transportation vehicles, whether boats, trains, planes andautomobiles, require high power density provided by internal combustionand/or propulsion engines. These engines require clean burning fuelswhich are generally in liquid form or, to a lesser extent, compressedgases. Liquid fuels are more portable due to their high energy densityand their ability to be pumped, which makes handling easier.

Currently, biomass provides the only renewable alternative for liquidtransportation fuels. Unfortunately, the progress in developing newtechnologies for producing liquid biofuels has been slow in developing,especially for liquid fuel products that fit within the currentinfrastructure. Although a variety of fuels can be produced from biomassresources, such as ethanol, methanol, biodiesel, Fischer-Tropsch dieseland kerosene, and gaseous fuels, such as hydrogen and methane, thesefuels can require either new distribution technologies and/or combustiontechnologies appropriate for their characteristics. The production ofthese fuels also tends to be expensive.

Ethanol, for example, is made by converting the carbohydrate frombiomass into sugar, which is then converted into ethanol in afermentation process. Ethanol is the most widely used biofuel today withcurrent capacity of 4.3 billion gallons per year based on starch crops,such as corn. Ethanol, however, has very substantial disadvantages withrespect its energy value as a fuel relative to the amount of energyneeded to produce it. Ethanol produced by fermentation contains largeamounts of water, typically comprising only about 5 percent of ethanolby volume in the water/alcohol fermentation product. The removal of thiswater is highly energy-consuming, and often requires the use of naturalgas as a heat source. Ethanol also has less energy content thangasoline, which means that it takes more fuel to go the same distance.Ethanol is very corrosive to fuel systems and cannot be transported inpetroleum pipelines. As a result, ethanol is transported over-the-roadin tank trucks, which increases its overall cost and energy consumption.When considering the total energy consumed by farm equipment,cultivation, planting, fertilizers, pesticides, herbicides,petroleum-based fungicides, irrigation systems, harvesting,transportation to processing plants, fermentation, distillation, drying,transport to fuel terminals and retail pumps, and lower ethanol fuelenergy content, the net energy content value added and delivered toconsumers is very small.

Biodiesel is another potential energy source. Biodiesel can be made fromvegetable oil, animal fats, waste vegetable oils, microalgae oils orrecycled restaurant greases, and is produced through a process in whichorganically derived oils are combined with alcohol (ethanol or methanol)in the presence of a catalyst to form ethyl or methyl ester. Thebiomass-derived ethyl or methyl esters can then be blended withconventional diesel fuel or used as a neat fuel (100% biodiesel).Biodiesel is also expensive to manufacture, and poses various issues inits use and combustion. For example, special handling may be required toavoid gelling in cold temperatures.

Biomass can also be gasified to produce a synthesis gas composedprimarily of hydrogen and carbon monoxide, also called syngas orbiosyngas. Syngas produced today is used directly to generate heat andpower, but several types of biofuels may be derived from syngas.Hydrogen can be recovered from syngas, or it can be catalyticallyconverted to methanol. The gas can also be run through a biologicalreactor to produce ethanol or converted using Fischer-Tropsch catalystinto a liquid stream with properties similar to diesel fuel, calledFischer-Tropsch diesel. These processes, however, tend to be expensive.

There exists a need for liquid fuel compositions which contain acomponent that is derivable from biomass and that is capable of use inthe current infrastructure, namely the same distribution system and thesame engines without the need for special modifications. There alsoexists a need for liquid fuel compositions which contain a componentthat is derivable from biomass that do not depend on microorganisms,enzymes or other expensive and delicate manufacturing processes.

SUMMARY OF THE INVENTION

The present invention provides a liquid fuel composition comprising adistillation fraction of a component having at least one C₄₊ compoundderived from a water-soluble oxygenated hydrocarbon prepared by a methodcomprising:

providing water and a water-soluble oxygenated hydrocarbon comprising aC₁₊O₁₊ hydrocarbon in an aqueous liquid phase and/or a vapor phase;

providing H₂;

catalytically reacting in the liquid and/or vapor phase the oxygenatedhydrocarbon with the H₂ in the presence of a deoxygenation catalyst at adeoxygenation temperature and deoxygenation pressure to produce anoxygenate comprising a C₁₊O₁₋₃ hydrocarbon in a reaction stream; and

catalytically reacting in the liquid and/or vapor phase the oxygenate inthe presence of a condensation catalyst at a condensation temperatureand condensation pressure to produce the C₄₊ compound,

wherein the C₄₊ compound comprises a member selected from the groupconsisting of C₄₊ alcohol, C₄₊ ketone, C₄₊ alkane, C₄₊ alkene, C₅₊cycloalkane, C₅₊ cycloalkene, aryl, fused aryl, and a mixture thereof;

wherein the liquid fuel composition is selected from:

a gasoline composition having an initial boiling point in the range offrom 15° C. to 70° C. (IP123), a final boiling point of at most 230° C.(IP123), a RON in the range of from 85 to 110 (ASTM D2699) and a MON inthe range of from 75 to 100 (ASTM D2700);

a diesel fuel composition having an initial boiling point in the rangeof from 130° C. to 230° C. (IP123), a final boiling point of at most410° C. (IP123) and a cetane number in the range of from 35 to 120 (ASTMD613); and

a kerosene composition having an initial boiling point in the range offrom 80 to 150° C., a final boiling point in the range of from 200 to320° C. and a viscosity at −20° C. in the range of from 0.8 to 10 mm²/s(ASTM D445).

The present invention also provides a gasoline composition comprising acomponent having at least one C₄₊ compound derivable from awater-soluble oxygenated hydrocarbon having a final boiling point in therange of from 150 to 220° C., a density at 15° C. in the range of from700 to 890 kg/m³, a sulphur content of at most 5 mg/kg, an oxygencontent of at most 3.5% wt., a RON in the range of from 80 to 110, and aMON in the range of from 70 to 100, wherein said gasoline compositionhas an initial boiling point in the range of from 15° C. to 70° C.(IP123), a final boiling point of at most 220° C. (IP123), a RON in therange of from 85 to 110 (ASTM D2699) and a MON in the range of from 75to 100 (ASTM D2700).

The present invention also provides a diesel fuel composition comprisinga component having at least one C₄₊ compound derivable from awater-soluble oxygenated hydrocarbon having t a T95 in the range of from220 to 380° C., a flash point in the range of from 30 to 70° C., adensity at 15° C. in the range of from 700 to 900 kg/m³, a sulphurcontent of at most 5 mg/kg, an oxygen content of at most 10% wt., and aviscosity at 40° C. in the range of from 0.5 to 6 cSt, wherein saiddiesel fuel composition has an initial boiling point in the range offrom 130° C. to 230° C. (IP123), a final boiling point of at most 410°C. (IP123) and a cetane number in the range of from 35 to 120 (ASTMD613).

The present invention also provides a kerosene composition comprising acomponent having at least one C₄₊ compound derivable from awater-soluble oxygenated hydrocarbon having an initial boiling point inthe range of from 120 to 215° C., a final boiling point in the range offrom 220 to 320° C., a density at 15° C. in the range of from 700 to 890kg/m³, a sulphur content of at most 0.1% wt., a total aromatics contentof at most 30% vol., a freeze point of −40° C. or lower, a smoke pointof at least 18 mm, a viscosity at −20° C. in the range of from 1 to 10cSt, and a specific energy content in the range of from 40 to 47 MJ/kg,wherein said kerosene composition has an initial boiling point in therange of from 80 to 150° C., a final boiling point in the range of from200 to 320° C. and a viscosity at −20° C. in the range of from 0.8 to 10mm²/s (ASTM D445).

The present invention also provides a method for preparing a liquid fuelcomposition according to the present invention, comprising admixing:

-   (a) a distillation fraction of a component having at least one C₄₊    compound derived from a water-soluble oxygenated hydrocarbon    prepared by a method comprising:    -   providing water and a water-soluble oxygenated hydrocarbon        comprising a C₁₊O₁₊ hydrocarbon in an aqueous liquid phase        and/or a vapor phase;    -   providing H₂;    -   catalytically reacting in the liquid and/or vapor phase the        oxygenated hydrocarbon with the H₂ in the presence of a        deoxygenation catalyst at a deoxygenation temperature and        deoxygenation pressure to produce an oxygenate comprising a        C₁₊O₁₋₃ hydrocarbon in a reaction stream; and    -   catalytically reacting in the liquid and/or vapor phase the        oxygenate in the presence of a condensation catalyst at a        condensation temperature and condensation pressure to produce        the C₄₊ compound,    -   wherein the C₄₊ compound comprises a member selected from the        group consisting of C₄₊ alcohol, C₄₊ ketone, C₄₊ alkane, C₄₊        alkene, C₅₊ cycloalkane, C₅₊ cycloalkene, aryl, fused aryl, and        a mixture thereof, with-   (b) at least one fuel component.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow diagram illustrating various production pathwaysassociated with the present invention.

FIG. 2 illustrates potential chemical routes that allow carbohydrates,such as sugars, to be converted to non-oxygenated hydrocarbons.

FIG. 3 is an illustration of various reaction pathways involved in thedeoxygenation of sorbitol to oxygenates and APR hydrogen.

FIG. 4 is an illustration of the thermodynamic equilibriums along thereaction pathway for converting acetone to 2-methyl pentane at 100° C.and 400° C.

FIG. 5 is a graph illustrating the equilibrium constants associated withthe intermediate reaction products and the overall conversion for thereaction of 2 moles of acetone with 3 moles of hydrogen to form 1 moleof 2-methylpentane and 2 moles of water.

FIG. 6 is a flow diagram illustrating a reactor system configured toallow for the recycle of hydrogen, oxygenates and oxygenatedhydrocarbons.

FIG. 7 is a flow diagram illustrating a reactor system configured toallow for the use of air or an oil as a temperature control element.

FIG. 8 a flow diagram illustrating a reactor system for the presentinvention.

FIG. 9 is a flow diagram illustrating a reactor system utilizing tworeactors.

FIG. 10 is a flow diagram illustrating a reactor system utilizing twofeedstock lines.

FIG. 11 is an illustration of a reactor useful in practicing the presentinvention.

FIG. 12 is a graph illustrating the carbon distribution ofmono-oxygenates produced from glycerol.

FIG. 13 is a graph illustrating the axial temperature profile for areactor when used to produce compounds from a feedstock of oxygenatedhydrocarbons.

FIG. 14 is a graph illustrating the percentage of feed carbon exiting asoxygenates from the conversion of an oxygenate feed stream to C₅₊compounds as a function of time.

FIG. 15 is a graph illustrating the percentage of feed carbon exiting asC₅₊ hydrocarbons from the conversion of an oxygenate feed stream as afunction of time.

FIG. 16 is a graph illustrating the percentage of feed carbon exiting asC₅₊ aromatic hydrocarbons from the conversion of an oxygenate feedstream as a function of time.

FIG. 17 is a graph showing the total weight percentage of paraffin andaromatic compounds derived from the conversion of a feed stream ofsucrose and xylose.

FIG. 18 is a graph illustrating the heating value of C₅₊ hydrocarbonsderived from the production of gasoline from sorbitol, as a percentageof the heating value of the feed.

FIG. 19 is a graph illustrating the percentage of carbon recovered asaromatic hydrocarbons from the production of gasoline from sorbitol,shown as a percentage of the carbon present in the feed.

DETAILED DESCRIPTION OF THE INVENTION

The liquid fuel compositions of the present invention comprise acomponent having at least one C₄₊ compound derived from a water-solubleoxygenated hydrocarbon. Preferably, the water-soluble oxygenatedhydrocarbon is derived from biomass.

Typically, the process of preparing the component having at least oneC₄₊ compound derived from a water-soluble oxygenated hydrocarbonproduces hydrocarbons, ketones and alcohols from biomass-derivedoxygenated hydrocarbons, such as sugars, sugar alcohols, cellulosics,lignocelluloses, hemicelluloses, saccharides and the like.

The component derived from a water-soluble oxygenated hydrocarboncomprises C₄₊ alkanes, C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊ cycloalkenes,aryls, fused aryls, C₄₊ alcohols, C₄₊ ketones, and mixtures thereof(collectively referred to herein as “C₄₊ compounds”). The C₄₊hydrocarbons typically have from 4 to 30 carbon atoms and may bebranched or straight chained alkanes or alkenes, or unsubstituted,mono-substituted or multi-substituted aromatics (aryls) or cycloalkanes.The C₄₊ alcohols and C₄₊ ketones may be cyclic, branched or straightchained, and have from 4 to 30 carbon atoms.

Lighter fractions, primarily C₄-C₉, may be separated for gasoline use.Moderate fractions, such as C₇-C₁₄, may be separated for kerosene, forexample for use in jet fuel, while heavier fractions, i.e., C₁₂-C₂₄, maybe separated for diesel fuel use. The heaviest fractions may be used aslubricants or cracked to produce additional gasoline and/or dieselfractions. The C₄₊ compounds derived from water-soluble oxygenatedhydrocarbons may also find use as industrial chemicals, such as xylene,whether as an intermediate or an end product.

Process of Preparing the Component Derived from a Water-SolubleOxygenated Hydrocarbon

The general process of preparing the component derived from awater-soluble oxygenated hydrocarbon is illustrated in FIG. 1. Afeedstock solution containing a water-soluble oxygenated hydrocarbonhaving one or more carbon atoms is reacted with hydrogen over adeoxygenation catalyst to produce oxygenates, and then the oxygenatesare reacted over a condensation catalyst under conditions of temperatureand pressure effective to cause a condensation reaction that producesthe C₄₊ compounds. The hydrogen may originate from any source, but ispreferably derived in situ or in parallel from biomass using aqueousphase reforming. The hydrogen and oxygenated hydrocarbons may also besupplemented with recycled hydrogen and oxygenated hydrocarbons derivedfrom the process. The oxygenated hydrocarbon may be a monosaccharide,disaccharide, polysaccharide, cellulose, hemicellulose, lignin, sugar,sugar alcohol or other polyhydric alcohols, or may be derived from thehydrogenation of a sugar, furfural, carboxylic acid, ketone, or furan,or the hydrogenolysis of a sugar, sugar alcohol, polysaccharide,monosaccharide, disaccharide or polyhydric alcohol.

One unique aspect about the process of preparing the component derivedfrom a water-soluble oxygenated hydrocarbon in the present invention isthat the C₄₊ compounds are derived from biomass components usingcatalytic processes instead of microorganisms, enzymes, high temperaturegasification or transesterification methods. The process of preparingthe component derived from a water-soluble oxygenated hydrocarbon in thepresent invention can also generate hydrogen in situ to avoid relianceon external hydrogen sources, such as hydrogen generated from the streamreforming of natural gas, or the electrolysis or thermolysis of water.The process of preparing the component derived from a water-solubleoxygenated hydrocarbon in the present invention also generates water,which may be recycled and used in upstream processes or returned to theenvironment. The process of preparing the component derived from awater-soluble oxygenated hydrocarbon in the present invention is alsoable to generate non-condensable fuel gases for purposes of providing aheat source within the reactor system or for external processes.

Carbohydrates are the most widely distributed, naturally occurringorganic compounds on Earth. Carbohydrates are produced duringphotosynthesis, a process in which the energy from the sun is convertedinto chemical energy by combining carbon dioxide with water to formcarbohydrates and oxygen:

The energy from sunlight is stored through this process as chemicalenergy in the form of carbohydrates in plants. The carbohydrates,especially when in a sugar form, are highly reactive compounds that arereadily oxidized by living material to generate energy, carbon dioxideand water. Plant materials store these carbohydrates either as sugars,starches, polymeric cellulose, and/or hemi-cellulose.

The presence of oxygen in the molecular structure of carbohydratescontributes to the reactivity of sugars in biological systems. Ethanolfermentation technology takes advantage of this highly reactive natureby forming ethanol at ambient temperatures. The fermentation technologyessentially de-functionalizes the highly reactive sugar to generate apartially oxidized hydrocarbon, ethanol. Ethanol, however, has verysubstantial disadvantages with respect its energy value as highlightedabove.

FIG. 2 shows potential chemical routes that allow carbohydrates, such assugars, to be converted to non-oxygenated hydrocarbons. Water solublecarbohydrates are known to react with hydrogen over catalyst(s) togenerate polyhydric alcohols, either by hydrogenation or hydrogenolysis.The hydrogen has historically been generated externally, i.e., fromnatural gas or by other processes, but can now be generated in situ orin parallel according to the present invention through the aqueous-phasereforming of the polyhydric alcohol.

The aqueous-phase reforming (APR) of the polyhydric alcohol proceedsthrough the formation of an aldehyde (shown in FIG. 2) where thealdehyde reacts over a catalyst with water to form hydrogen, carbondioxide, and a smaller polyhydric alcohol. The polyhydric alcohol canfurther react with hydrogen over a catalyst through a series ofdeoxygenation reactions to form either alcohol, ketone, or aldehydesspecies that can undergo condensation reactions to form either largercarbon number straight chain compounds, branched chain compounds, orcyclic compounds. The condensation reactions can be either acidcatalyzed, base catalyzed, or both acid and base catalyzed. Theresulting compounds may be hydrocarbons or hydrocarbons containingoxygen, the oxygen of which can be removed through the reaction withhydrogen over a catalyst. The resulting condensed products include C₄₊alcohols, C₄₊ ketones, C₄₊ alkanes, C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊cycloalkenes, aryls, fused aryls, and mixtures thereof. The mixtures canbe fractionated and blended to produce the appropriate mixtures ofmolecules typically used in gasoline, kerosene (for example as jetfuel), or diesel fuels.

The de-functionalization begins by reacting the glucose with hydrogen ineither a hydrogenation reaction or hydrogenolysis reaction to convertthe cyclic sugar molecule to its corresponding linear alcohol, sorbitol,or lower polyhydric alcohols, such as glycerol, propylene glycol,ethylene glycol, xylitol, among others. As indicated above, the hydrogenmay be from any source, but is preferably hydrogen generated in situ byaqueous phase reforming or excess hydrogen recycled from the reactorsystem.

During the aqueous phase reforming process, the carbohydrate firstundergoes dehydrogenation to provide adsorbed intermediates, prior tocleavage of C—C or C—O bonds. Subsequent cleavage of C—C bonds leads tothe formation of CO and H₂, with the CO then reacting with water to formCO₂ and H₂ by the water-gas shift reaction. Various APR methods andtechniques are described in U.S. Pat. Nos. 6,699,457; 6,964,757 and6,964,758; and U.S. patent application Ser. No. 11,234,727 (all toCortright et al., and entitled “Low-Temperature Hydrogen Production fromOxygenated Hydrocarbons”); and U.S. Pat. No. 6,953,873 (to Cortright etal., and entitled “Low Temperature Hydrocarbon Production fromOxygenated Hydrocarbons”); and WO 2007/075476 A2 (to Cortright et al.,and entitled “Catalyst and Methods for Reforming Oxygenated Compounds”),all of which are incorporated herein by reference. The term “aqueousphase reforming” and “APR” shall generically denote the reforming ofoxygenated hydrocarbons and water to yield hydrogen and carbon dioxide,regardless of whether the reactions takes place in the gaseous phase orin the condensed liquid phase. “APR H₂” shall generically refer to thehydrogen produced by the APR process.

The resulting oxygenated hydrocarbon, namely the sorbitol or glycerol,propylene glycol, ethylene glycol, xylitol, etc., are furtherdefunctionalized through deoxygenation reactions to form oxygenates,such as alcohols, ketones, aldehydes, furans, diols, triols, hydroxycarboxylic acids, and carboxylic acids for use in later condensationreactions. FIG. 3 illustrates various reaction pathways involved in thedeoxygenation of sorbitol to oxygenates and APR hydrogen. In general,without being limited to any particular theory, it is believed that thedeoxygenation reactions involves a combination of various differentreaction pathways, including without limitation: hydrodeoxygenation,consecutive dehydration-hydrogenation, hydrogenolysis, hydrogenation anddehydration reactions, resulting in the removal of oxygen from theoxygenated hydrocarbon to arrive at a hydrocarbon molecule having thegeneral formula C₁₊O₁₋₃.

The oxygenates produced are then converted into C₄₊ compounds bycondensation. Without being limited to any specific theories, it isbelieved that the acid condensation reactions generally consist of aseries of steps involving: (a) the dehydration of oxygenates to olefins;(b) oligomerization of the olefins; (c) cracking reactions; (d)cyclization of larger olefins to form aromatics; (e) paraffinisomerization; and (f) hydrogen-transfer reactions to form paraffins.Basic condensation reactions are believed to generally consist of aseries of steps involving: (1) aldol condensation to form aβ-hydroxyketone or β-hydroxyaldehyde; (2) dehydration of theβ-hydroxyketone or β-hydroxyaldehyde to form a conjugated enone; (3)hydrogenation of the conjugated enone to form a ketone or aldehyde,which may participate in further condensation reactions or conversion toan alcohol or hydrocarbon; and (4) hydrogenation of carbonyls toalcohols, or vice-versa. Acid-base condensation reactions are believedto generally involve any of the previous acidic and/or basic reactionssteps.

In certain embodiments, the condensation reactions occur at typicalcondensation temperatures and pressures. However, in variousembodiments, it may also be more favorable to conduct the condensationreactions at temperature and/or pressure conditions that are elevated ascompared to typical condensation processes. Generally, conductingcondensation reactions under elevated conditions results in unfavorablethermodynamics that limit the extent of conversion to condensationproducts. The present invention has revealed that conducting thereaction with the condensation catalysts and at the temperatures andpressures described below overcomes these limitations and unexpectedlypromotes an immediate conversion of the condensation products tohydrocarbons, ketones and alcohols. The conversion, in turn, removes thecondensation products from the reaction, thereby overcoming thethermodynamic limitations of the system to allow additional condensationreactions to occur. Elevated temperature and/or pressure conditions alsoavoid excessive conversion of the oxygenates directly to theircorresponding hydrocarbons. The process also has the added benefit ofallowing for the condensation reactions, deoxygenation reactions and APRreactions to occur in a single reactor and under steady-stateequilibrium.

For any given reaction, the free energy change is indicative of thefavorability of the forward reaction. The more negative the free energychange, the more favorable the reaction. As a result, reactionsassociated with a highly negative change in free energy are generallyfavorable and have the potential to exhibit high conversions to reactionproducts. Conversely, reactions associated with positive changes in freeenergy are not favorable and are inherently limited in the extent towhich reactants are converted to products. As an illustration, FIG. 4shows the free energy changes associated with steps along the reactionpathway for converting acetone and hydrogen to a C₆ hydrocarbon(2-methylpentane) and water at 100° C. and 400° C. The known free energylevels of the stable intermediates derived along this pathway are shownwith a solid line. The first step in the reaction pathway is the aldolcondensation of two molecules of acetone to form one molecule ofdiacetone alcohol. The reaction at the lower temperature (100° C.) has afree energy change of −53 KJ/mole and is thermodynamically favored,while the reaction at the higher temperature (400° C.) is less favorabledue to a free energy change of −10 KJ/mole. The implication is that themaximum conversion of pure acetone to diacetone alcohol for this stepdecreases as the temperature is increased (greater than 99% theoreticalmaximal conversion at 100° C. at atmospheric pressure, to only 15% at400° C. at atmospheric pressure). Accordingly, the thermodynamicequilibrium limitation imposes an absolute limit to the amount ofdiacetone alcohol that may be produced under given conditions and in theabsence of other reactions. This is further illustrated in FIG. 5, whichprovides the equilibrium constants associated with the intermediatereaction products and the overall conversion for the reaction of 2 molesof acetone with 3 moles of hydrogen to form 1 mole of 2-methylpentaneand 2 moles of water. It can be seen that the equilibrium constant forthe conversion of acetone to diacetone alcohol decreases with increasingtemperature.

The present invention obviates this issue by immediately converting thecondensation product to a compound that provides a more favorablereaction environment. In the case above, by removing the diacetonealcohol from the reaction mixture through a dehydration reaction thatforms mesityl oxide, additional diacetone alcohol can be formed. Inparticular, the combination of a condensation and dehydration step toprovide mesityl oxide and water from acetone provides a slightly morefavorable reaction environment. As illustrated in FIG. 5, the conversionof acetone to mesityl oxide and water is slightly more favorable at thehigher temperatures.

The total reaction system pressure also has a beneficial effect on themaximal theoretical extent to which reactant may form a product.Considering the condensation reaction example above, the conversion ofacetone to diacetone alcohol is limited to 15% at 400° C. at atmosphericpressure with pure acetone feed. By increasing the system pressure to600 psi gauge pressure, the equilibrium conversion shifts so that up to76% conversion may be achieved at the same temperature. For reactionsexhibiting a net decrease in the number of moles of product as comparedto the moles of reactant, an increase in system pressure (with all otherconditions held constant) will act to increase the equilibrium productconversion. For the overall conversion of ketones to hydrocarbons, thereis typically a net decrease in the moles of product compared to themoles of reactant, thus higher reaction pressures would lead to higherpotential equilibrium conversions.

The process of preparing the component derived from a water-solubleoxygenated hydrocarbon in the present invention strikes a balance withthe above thermodynamic limitations by operating with condensationcatalysts and at temperature and pressure conditions that offset anyreduction in the production of condensation products with an increase inthe conversion to other downstream products. The kinetics of the entiresystem is also more favorable such that products may be producedcontinuously and at a more desirable rate. In terms of scaled-upproduction, after start-up, the reactor systems may be processcontrolled, and the reactions could proceed at steady-state equilibrium.

Oxygenates

The C₄₊ compounds are derived from oxygenates. As used herein inrelation to the process of preparing the component derived from awater-soluble oxygenated hydrocarbon, “oxygenates” generically refers tohydrocarbon compounds having 1 or more carbon atoms and between 1 and 3oxygen atoms (referred to herein as C₁₊O₁₋₃ hydrocarbons), such asalcohols, ketones, aldehydes, furans, hydroxy carboxylic acids,carboxylic acids, diols and triols. Preferably, the oxygenates have from1 to 6 carbon atoms, or 2 to 6 carbon atoms, or 3 to 6 carbon atoms.Alcohols may include, without limitation, primary, secondary, linear,branched or cyclic C₁₊ alcohols, such as methanol, ethanol, n-propylalcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol,pentanol, cyclopentanol, hexanol, cyclohexanol,2-methyl-cyclopentanonol, heptanol, octanol, nonanol, decanol,undecanol, dodecanol, and isomers thereof. The ketones may include,without limitation, hydroxyketones, cyclic ketones, diketones, acetone,propanone, 2-oxopropanal, butanone, butane-2,3-dione,3-hydroxybutan-2-one, pentanone, cyclopentanone, pentane-2,3-dione,pentane-2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone,heptanone, octanone, nonanone, decanone, undecanone, dodecanone,methylglyoxal, butanedione, pentanedione, diketohexane, and isomersthereof. The aldehydes may include, without limitation,hydroxyaldehydes, acetaldehyde, propionaldehyde, butyraldehyde,pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal,dodecanal, and isomers thereof. The carboxylic acids may include,without limitation, formic acid, acetic acid, propionic acid, butanoicacid, pentanoic acid, hexanoic acid, heptanoic acid, isomers andderivatives thereof, including hydroxylated derivatives, such as2-hydroxybutanoic acid and lactic acid. The diols may include, withoutlimitation, ethylene glycol, propylene glycol, 1,3-propanediol,butanediol, pentanediol, hexanediol, heptanediol, octanediol,nonanediol, decanediol, undecanediol, dodecanediol, and isomers thereof.The triols may include, without limitation, glycerol, 1,1,1tris(hydroxymethyl)-ethane (trimethylolethane), trimethylolpropane,hexanetriol, and isomers thereof. Furans and furfurals include, withoutlimitation, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol,2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-methyl furan,2-ethyl-tetrahydrofuran, 2-ethyl furan, hydroxylmethylfurfural,3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 2,5-dimethyl furan,5-hydroxymethyl-2(5H)-furanone,dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furoic acid,dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol,1-(2-furyl)ethanol, hydroxymethyltetrahydrofurfural, and isomersthereof.

The oxygenates may originate from any source, but are preferably derivedfrom biomass. As used herein, the term “biomass” refers to, withoutlimitation, organic materials produced by plants (such as leaves, roots,seeds and stalks), and microbial and animal metabolic wastes. Commonsources of biomass include: (1) agricultural wastes, such as cornstalks, straw, seed hulls, sugarcane leavings, bagasse, nutshells, andmanure from cattle, poultry, and hogs; (2) wood materials, such as woodor bark, sawdust, timber slash, and mill scrap; (3) municipal waste,such as waste paper and yard clippings; and (4) energy crops, such aspoplars, willows, switch grass, alfalfa, prairie bluestream, corn,soybean, and the like. The term also refers to the primary buildingblocks of the above, namely, saccharides, lignin, cellulosics,hemicellulose and starches, among others.

Oxygenates from biomass may be produced by any known method. Suchmethods include fermentation technologies using enzymes ormicroorganisms, Fischer-Tropsch reactions to produce C₂₋₁₀ alphaalcohols, and pyrolysis technologies to produce alcohols from oil, amongothers. In one embodiment, the oxygenates are produced using catalyticreforming technologies, such as the BioForming™ technology developed byVirent Energy Systems, Inc. (Madison, Wis.).

Oxygenated Hydrocarbons

In one embodiment, the oxygenates are derived from the catalyticreforming of oxygenated hydrocarbons. The oxygenated hydrocarbons may beany water-soluble oxygenated hydrocarbon having one or more carbon atomsand at least one oxygen atom (referred to herein as C₁₊O₁₊hydrocarbons). Preferably, the oxygenated hydrocarbon has 2 to 12 carbonatoms (C₁₋₁₂O₁₋₁₁ hydrocarbon), and more preferably 2 to 6 carbon atoms(C₁₋₆O₁₋₆ hydrocarbon). The oxygenated hydrocarbon may also have anoxygen-to-carbon ratio ranging from 0.5:1 to 1.5:1, including ratios of0.75:1.0, 1.0:1.0, 1.25:1.0, 1.5:1.0, and other ratios between. In oneexample, the oxygenated hydrocarbon has an oxygen-to-carbon ratio of1:1. Nonlimiting examples of preferred water-soluble oxygenatedhydrocarbons include monosaccharides, disaccharides, polysaccharides,sugar, sugar alcohols, alditols, ethanediol, ethanedione, acetic acid,propanol, propanediol, propionic acid, glycerol, glyceraldehyde,dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, butanediols,butanoic acid, aldotetroses, tautaric acid, aldopentoses, aldohexoses,ketotetroses, ketopentoses, ketohexoses, alditols, hemicelluloses,cellulosic derivatives, lignocellulosic derivatives, starches, polyolsand the like. Preferably, the oxygenated hydrocarbon includes sugar,sugar alcohols, saccharides and other polyhydric alcohols. Morepreferably, the oxygenated hydrocarbon is a sugar, such as glucose,fructose, sucrose, maltose, lactose, mannose or xylose, or a sugaralcohol, such as arabitol, erythritol, glycerol, isomalt, lactitol,malitol, mannitol, sorbitol, xylitol, ribitol, or glycol.

Oxygenated hydrocarbons shall also refer to and include alcohols derivedby hydrogenation or hydrogenolysis of any of the foregoing. In certainembodiments, it may be preferable to convert the starting oxygenatedhydrocarbon to another oxygenated hydrocarbon form that can be morereadily converted to the desired oxygenates (e.g., primary, secondary,tertiary or polyhydric alcohols). For instance, some sugars may notconvert as efficiently to oxygenates as compared to their correspondingsugar alcohol derivatives. It may therefore be desirable to convert thestarting material, such as a sugar, furfural, carboxylic acid, ketone,or furan, into its corresponding alcohol derivative, such as byhydrogenation, or to smaller alcohol molecules, such as byhydrogenolysis.

Various processes are known for hydrogenating sugars, furfurals,carboxylic acids, ketones, and furans to their corresponding alcoholform, including those disclosed by: B. S. Kwak et al. (WO2006/093364A1and WO 2005/021475A1), involving the preparation of sugar alditols frommonosaccharides by hydrogenation over a ruthenium catalyst; and Elliotet al. (U.S. Pat. Nos. 6,253,797 and 6,570,043), disclosing the use of anickel and rhenium free ruthenium catalyst on a more than 75% rutiletitania support to convert sugars to sugar alcohols, all incorporatedherein by reference. Other suitable ruthenium catalysts are described byArndt et al. in published U.S. patent application 2006/0009661 (filedDec. 3, 2003), and Arena in U.S. Pat. Nos. 4,380,679 (filed Apr. 12,1982), 4,380,680 (filed May 21, 1982), 4,503,274 (filed Aug. 8, 1983),4,382,150 (filed Jan. 19, 1982), and 4,487,980 (filed Apr. 29, 1983),all incorporated herein by reference. The hydrogenation catalystgenerally includes Cu, Re, Ni, Fe, Co, Ru, Pd, Rh, Pt, Os, Ir, andalloys or combinations thereof, either alone or with promoters such asW, Mo, Au, Ag, Cr, Zn, Mn, Sn, B, P, Bi, and alloys or combinationsthereof. The hydrogenation catalyst may also include any one of thesupports further described below, and depending on the desiredfunctionality of the catalyst. Other effective hydrogenation catalystmaterials include either supported nickel or ruthenium modified withrhenium. In general, the hydrogenation reaction is carried out athydrogenation temperatures of between about 80° C. to 250° C., andhydrogenation pressures in the range of about 100 psig to 2000 psig. Thehydrogen used in the reaction may include in situ generated H₂, externalH₂, recycled H₂, or a combination thereof.

The hydrogenation catalyst may also include a supported Group VIII metalcatalyst and a metal sponge material, such as a sponge nickel catalyst.Activated sponge nickel catalysts (e.g., Raney nickel) are a well-knownclass of materials effective for various hydrogenation reactions. Onetype of sponge nickel catalyst is the type A7063 catalyst available fromActivated Metals and Chemicals, Inc., Sevierville, Tenn. The type A7063catalyst is a molybdenum promoted catalyst, typically containingapproximately 1.5% molybdenum and 85% nickel. The use of the spongenickel catalyst with a feedstock comprising xylose and dextrose isdescribed by M. L. Cunningham et al. in U.S. Pat. No. 6,498,248, filedSep. 9, 1999, incorporated herein by reference. The use of a Raneynickel catalyst with hydrolyzed corn starch is also described in U.S.Pat. No. 4,694,113, filed Jun. 4, 1986, and incorporated herein byreference.

The preparation of suitable Raney nickel hydrogenation catalysts isdescribed by A. Yoshino et al. in published U.S. patent application2004/0143024, filed Nov. 7, 2003, incorporated herein by reference. TheRaney nickel catalyst may be prepared by treating an alloy ofapproximately equal amounts by weight of nickel and aluminum with anaqueous alkali solution, e.g., containing about 25 wt. % of sodiumhydroxide. The aluminum is selectively dissolved by the aqueous alkalisolution leaving particles having a sponge construction and composedpredominantly of nickel with a minor amount of aluminum. Promotermetals, such as molybdenum or chromium, may be also included in theinitial alloy in an amount such that about 1-2 wt. % remains in thesponge nickel catalyst.

In another embodiment, the hydrogenation catalyst is prepared byimpregnating a suitable support material with a solution of ruthenium(III) nitrosylnitrate, ruthenium (III) nitrosylnitrate, or ruthenium(III) chloride in water to form a solid that is then dried for 13 hoursat 120° C. in a rotary ball oven (residual water content is less than 1%by weight). The solid is then reduced at atmospheric pressure in ahydrogen stream at 300° C. (uncalcined) or 400° C. (calcined) in therotary ball furnace for 4 hours. After cooling and rendering inert withnitrogen, the catalyst may then be passivated by passing over 5% byvolume of oxygen in nitrogen for a period of 120 minutes.

In yet another embodiment, the hydrogenation reaction is performed usinga catalyst comprising a nickel-rhenium catalyst or a tungsten-modifiednickel catalyst. One example of a suitable hydrogenation catalyst is thecarbon-supported nickel-rhenium catalyst composition disclosed by Werpyet al. in U.S. Pat. No. 7,038,094, filed Sep. 30, 2003, and incorporatedherein by reference.

In other embodiments, it may also be desirable to convert the startingoxygenated hydrocarbon, such as a sugar, sugar alcohol or otherpolyhydric alcohol, to a smaller molecule that can be more readilyconverted to the desired oxygenates, such as by hydrogenolysis. Suchsmaller molecules may include primary, secondary, tertiary or polyhydricalcohols having less carbon atoms than the originating oxygenatedhydrocarbon. Various processes are known for such hydrogenolysisreactions, including those disclosed by: Werpy et al. in U.S. Pat. Nos.6,479,713 (filed Oct. 23, 2001), 6,677,385 (filed Aug. 6, 2002),6,6841,085 (filed Oct. 23, 2001) and 7,083,094 (filed Sep. 30, 2003),all incorporated herein by reference and describing the hydrogenolysisof and 6 carbon sugars and sugar alcohols to propylene glycol, ethyleneglycol and glycerol using a rhenium-containing multi-metallic catalyst.Other systems include those described by Arena in U.S. Pat. No.4,401,823 (filed May 18, 1981) directed to the use of a carbonaceouspyropolymer catalyst containing transition metals (such as chromium,molybdenum, tungsten, rhenium, manganese, copper, cadmium) or Group VIIImetals (such as iron, cobalt, nickel, platinum, palladium, rhodium,ruthenium, iridium and osmium) to produce alcohols, acids, ketones, andethers from polyhydroxylated compounds, such as sugars and sugaralcohols, and U.S. Pat. No. 4,496,780 (filed Jun. 22, 1983) directed tothe use of a catalyst system having a Group VIII noble metal on a solidsupport with an alkaline earth metal oxide to produce glycerol, ethyleneglycol and 1,2-propanediol from carbohydrates, each incorporated hereinby reference. Another system includes that described by Dubeck et al. inU.S. Pat. No. 4,476,331 (filed Sep. 6, 1983) directed to the use of asulfide-modified ruthenium catalyst to produce ethylene glycol andpropylene glycol from larger polyhydric alcohols, such as sorbitol, alsoincorporated herein by reference. Other systems include those describedby Saxena et al., “Effect of Catalyst Constituents on (Ni, Mo andCu)/Kieselguhr-Catalyzed Sucrose Hydrogenolysis,” Ind. Eng. Chem. Res.44, 1466-1473 (2005), describing the use of Ni, W, and Cu on akieselguhr support, incorporated herein by reference.

In one embodiment, the hydrogenolysis catalyst includes Cr, Mo, W, Re,Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, or Os, and alloys orcombinations thereof, either alone or with promoters such as Au, Ag, Cr,Zn, Mn, Sn, Bi, B, O and alloys or combinations thereof. Other effectivehydrogenolysis catalyst materials may include the above metals combinedwith an alkaline earth metal oxide or adhered to catalytically activesupport, such as kieselguhr, or any one of the supports furtherdescribed below.

The process conditions for carrying out the hydrogenolysis reaction willvary depending on the type of feedstock and desired products. Ingeneral, the hydrogenolysis reaction is conducted at temperatures of atleast 110° C., or between 110° C. and 300° C., or between 170° C. and240° C. The reaction should also be conducted under basic conditions,preferably at a pH of about 8 to about 13, or at a pH of about 10 toabout 12. The reaction should also be conducted at pressures of betweenabout 10 psig and 2400 psig, or between about 250 psig and 2000 psig, orbetween about 700 psig and 1600 psig.

The hydrogen used in the reaction may include in situ generated H₂,external H₂, recycled H₂, or a combination thereof.

Production of Oxygenates

The oxygenates are prepared by reacting an aqueous feedstock solutioncontaining water and the water soluble oxygenated hydrocarbons withhydrogen over a catalytic material to produce the desired oxygenates.Preferably, the hydrogen is generated in situ using aqueous phasereforming (in situ generated H₂ or APR H₂), or a combination of APR H₂,external H₂ or recycled H₂, or just simply external H₂ or recycled H₂.The term “external H₂”refers to hydrogen that does not originate fromthe feedstock solution, but is added to the reactor system from anexternal source. The term “recycled H₂” refers to unconsumed hydrogenthat originates from the feedstock solution, and which is collected andthen recycled back into the reactor system for further use. External H₂and recycled H₂ may also be referred to collectively or individually as“supplemental H₂.” In general, supplemental H₂ may be added for purposesof supplementing the APR hydrogen, or to substitute the inclusion of anAPR hydrogen production step, or to increase the reaction pressurewithin the system, or to increase the molar ratio of hydrogen to carbonand/or oxygen in order to enhance the production yield of certainreaction product types, such as ketones and alcohols.

In processes utilizing APR H₂, the oxygenates are prepared bycatalytically reacting a portion of the aqueous feedstock solutioncontaining water and the water soluble oxygenated hydrocarbons in thepresence of an APR catalyst at a reforming temperature and reformingpressure to produce the APR H₂, and catalytically reacting the APR H₂(and recycled H₂ and/or external H₂) with a portion of the feedstocksolution in the presence of a deoxygenation catalyst at a deoxygenationtemperature and deoxygenation pressure to produce the desiredoxygenates. In systems utilizing recycled H₂ or external H₂ as ahydrogen source, the oxygenates are simply prepared by catalyticallyreacting the recycled H₂ and/or external H₂ with the feedstock solutionin the presence of the deoxygenation catalyst at the deoxygenationtemperatures and pressures. In each of the above, the oxygenates mayalso include recycled oxygenates (recycled C₁₊O₁₋₃ hydrocarbons). Unlessotherwise indicated, any discussions of APR catalysts and deoxygenationcatalysts are non-limiting examples of suitable catalytic materials.

The deoxygenation catalyst is preferably a heterogeneous catalyst havingone or more materials capable of catalyzing a reaction between hydrogenand the oxygenated hydrocarbon to remove one or more of the oxygen atomsfrom the oxygenated hydrocarbon to produce alcohols, ketones, aldehydes,furans, carboxylic acids, hydroxy carboxylic acids, diols and triols. Ingeneral, the materials will be adhered to a support and may include,without limitation, Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo,Ag, Au, alloys and combinations thereof. The deoxygenation catalyst mayinclude these elements alone or in combination with one or more Mn, Cr,Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga,In, Tl, and combinations thereof. In one embodiment, the deoxygenationcatalyst includes Pt, Ru, Cu, Re, Co, Fe, Ni, W or Mo. In yet anotherembodiment, the deoxygenation catalyst includes Fe or Re and at leastone transition metal selected from Ir, Ni, Pd, P, Rh, and Ru. In anotherembodiment, the catalyst includes Fe, Re and at least Cu or one GroupVIIIB transition metal. The support may be any one of the supportsfurther described below, including a nitride, carbon, silica, alumina,zirconia, titania, vanadia, ceria, zinc oxide, chromia, boron nitride,heteropolyacids, kieselguhr, hydroxyapatite, and mixtures thereof. Thedeoxygenation catalyst may also be atomically identical to the APRcatalyst or the condensation catalyst.

The deoxygenation catalyst may also be a bi-functional catalyst. Forexample, acidic supports (e.g., supports having low isoelectric points)are able to catalyze dehydration reactions of oxygenated compounds,followed by hydrogenation reactions on metallic catalyst sites in thepresence of H₂, again leading to carbon atoms that are not bonded tooxygen atoms. The bi-functional dehydration/ hydrogenation pathwayconsumes H₂ and leads to the subsequent formation of various polyols,diols, ketones, aldehydes, alcohols and cyclic ethers, such as furansand pyrans. Catalyst examples include tungstated zirconia, titaniazirconia, sulfated zirconia, acidic alumina, silica-alumina, zeolitesand heteropolyacid supports. Heteropolyacids are a class of solid-phaseacids exemplified by such species as H_(3+x)PMo_(12−x)V_(x)O₄₀,H₄SiW₁₂O₄₀, H₃PW₁₂O₄₀, and H₆P2W₁₈O₆₂. Heteropolyacids are solid-phaseacids having a well-defined local structure, the most common of which isthe tungsten-based Keggin structure.

Loading of the first element (i.e., Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd,Ni, W, Os, Mo, Ag, Au, alloys and combinations thereof) is in the rangeof 0.25 wt % to 25 wt % on carbon, with weight percentages of 0.10% and0.05% increments between, such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%,5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio ofthe second element (i.e., Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc,Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and combinations thereof) isin the range of 0.25-to-1 to 10-to-1, including any ratios between, suchas 0.50, 1.00, 2.50, 5.00, and 7.50-to-1. If the catalyst is adhered toa support, the combination of the catalyst and the support is from 0.25wt % to 10 wt % of the primary element.

To produce oxygenates, the oxygenated hydrocarbon is combined with waterto provide an aqueous feedstock solution having a concentrationeffective for causing the formation of the desired reaction products.The water-to-carbon ratio on a molar basis is preferably from about0.5:1 to about 100:1, including ratios such as 1:1, 2:1, 3:1, 4:1, 5:1,6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 25:1, 50:1 75:1, 100:1, and any ratiosthere-between. The feedstock solution may also be characterized as asolution having at least 1.0 weight percent (wt %) of the total solutionas an oxygenated hydrocarbon. For instance, the solution may include oneor more oxygenated hydrocarbons, with the total concentration of theoxygenated hydrocarbons in the solution being at least about 1%, 5%,10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or greater by weight, includingany percentages between, and depending on the oxygenated hydrocarbonsused. In one embodiment, the feedstock solution includes at least about10%, 20%, 30%, 40%, 50%, or 60% of a sugar, such as glucose, fructose,sucrose or xylose, or a sugar alcohol, such as sorbitol, mannitol,glycerol or xylitol, by weight. Water-to-carbon ratios and percentagesoutside of the above stated ranges are also included. Preferably thebalance of the feedstock solution is water. In some embodiments, thefeedstock solution consists essentially of water, one or more oxygenatedhydrocarbons and, optionally, one or more feedstock modifiers describedherein, such as alkali or hydroxides of alkali or alkali earth salts oracids. The feedstock solution may also include recycled oxygenatedhydrocarbons recycled from the reactor system. The feedstock solutionmay also contain negligible amounts of hydrogen, preferably less thanabout 1.5 mole of hydrogen per mole of feedstock. In the preferredembodiments, hydrogen is not added to the feedstock solution.

The feedstock solution is reacted with hydrogen in the presence of thedeoxygenation catalyst at deoxygenation temperature and pressureconditions, and weight hourly space velocity, effective to produce thedesired oxygenates. The specific oxygenates produced will depend onvarious factors, including the feedstock solution, reaction temperature,reaction pressure, water concentration, hydrogen concentration, thereactivity of the catalyst, and the flow rate of the feedstock solutionas it affects the space velocity (the mass/volume of reactant per unitof catalyst per unit of time), gas hourly space velocity (GHSV), andweight hourly space velocity (WHSV). For example, an increase in flowrate, and thereby a reduction of feedstock exposure to the catalystsover time, will limit the extent of the reactions which may occur,thereby causing increased yield for higher level diols and triols, witha reduction in ketone and alcohol yields.

The deoxygenation temperature and pressure are preferably selected tomaintain at least a portion of the feedstock in the liquid phase at thereactor inlet. It is recognized, however, that temperature and pressureconditions may also be selected to more favorably produce the desiredproducts in the vapor-phase. In general, the reaction should beconducted at process conditions wherein the thermodynamics of theproposed reaction are favorable. For instance, the minimum pressurerequired to maintain a portion of the feedstock in the liquid phase willlikely vary with the reaction temperature. As temperatures increase,higher pressures will generally be required to maintain the feedstock inthe liquid phase, if desired. Pressures above that required to maintainthe feedstock in the liquid phase (i.e., vapor-phase) are also suitableoperating conditions.

In condensed phase liquid reactions, the pressure within the reactormust be sufficient to maintain the reactants in the condensed liquidphase at the reactor inlet. For liquid phase reactions, the reactiontemperature may be from about 80° C. to 300° C., and the reactionpressure from about 72 psig to 1300 psig. In one embodiment, thereaction temperature is between about 120° C. and 300° C., or betweenabout 200° C. and 280° C., or between about 220° C. and 260° C., and thereaction pressure is preferably between about 72 and 1200 psig, orbetween about 145 and 1200 psig, or between about 200 and 725 psig, orbetween about 365 and 700 psig, or between about 600 and 650 psig.

For vapor phase reactions, the reaction should be carried out at atemperature where the vapor pressure of the oxygenated hydrocarbon is atleast about 0.1 atm (and preferably a good deal higher), and thethermodynamics of the reaction are favorable. This temperature will varydepending upon the specific oxygenated hydrocarbon compound used, but isgenerally in the range of from about 100° C. to 600° C. for vapor phasereactions. Preferably, the reaction temperature is between about 120° C.and about 300° C., or between about 200° C. and about 280° C., orbetween about 220° C. and about 260° C.

In another embodiment, the deoxygenation temperature is between about100° C. and 400° C., or between about 120° C. and 300° C., or betweenabout 200° C. and 280° C., and the reaction pressure is preferablybetween about 72 and 1300 psig, or between about 72 and 1200 psig, orbetween about 200 and 725 psig, or between about 365 and 700 psig.

A condensed liquid phase method may also be performed using a modifierthat increases the activity and/or stability of the catalyst system. Itis preferred that the water and the oxygenated hydrocarbon are reactedat a suitable pH of from about 1.0 to about 10.0, including pH values inincrements of 0.1 and 0.05 between, and more preferably at a pH of fromabout 4.0 to about 10.0. Generally, the modifier is added to thefeedstock solution in an amount ranging from about 0.1% to about 10% byweight as compared to the total weight of the catalyst system used,although amounts outside this range are included within the presentinvention.

In general, the reaction should be conducted under conditions where theresidence time of the feedstock solution over the catalyst isappropriate to generate the desired products. For example, the WHSV forthe reaction may be at least about 0.1 gram of oxygenated hydrocarbonper gram of catalyst per hour, and more preferably the WHSV is about 0.1to 40.0 g/g hr, including a WHSV of about 0.25, 0.5, 0.75, 1.0, 1.0,1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4,2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8,3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40 g/g hr.

The hydrogen used in the deoxygenation reaction is preferably in-situgenerated H₂, but may also be external or recycled H₂. When present, theamount of external H₂ is preferably provided sparingly. Most preferably,the amount of external H₂ is provided in amounts that provide less thanone hydrogen atom per oxygen atom in all of the oxygenated hydrocarbonsin the feedstock stream prior to contacting the deoxygenation catalyst.For example, the molar ratio between the external H₂ and the totalwater-soluble oxygenated hydrocarbons in the feedstock solution ispreferably selected to provide no more than one hydrogen atom per oxygenatom in the oxygenated hydrocarbon. The molar ratio of the oxygenatedhydrocarbons in the feedstock to the external H₂ introduced to thefeedstock is also preferably not more than 1:1, or more preferably up to2:1, 3:1, 5:1, 10:1, 20:1 or greater (including 4:1, 6:1, 7:1, 8:1, 9:1,11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1 and 19:1). The amount(moles) of external H₂ introduced to the feedstock is between 0-100%,0-95%, 0-90%, 0-85%, 0-80%, 0-75%, 0-70%, 0-65%, 0-60%, 0-55%, 0-50%,0-45%, 0-40%, 0-35%, 0-30%, 0-25%, 0-20%, 0-15%, 0-10%, 0-5%, 0-2%, or0-1% of the total number of moles of the oxygenated hydrocarbon(s) inthe feedstock, including all intervals between. When the feedstocksolution, or any portion thereof, is reacted with APR hydrogen andexternal H₂, the molar ratio of APR hydrogen to external H₂ is at least1:20; 1:15, 1:10, 1:5; 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1, 20:1,and ratios between (including 4:1, 6:1, 7:1, 8:1, 9:1, 11:1, 12:1, 13:1,14:1, 15:1, 16:1, 17:1, 18:1 and 19:1, and vice-versa). Preferably, theoxygenated hydrocarbon is reacted with H₂ in the presence of aninsignificantly effective amount of external H₂.

The amount of external H₂ (or supplemental H₂) added may be calculatedby considering the concentration of the oxygenated hydrocarbons in thefeedstock solution. Preferably, the amount of external H₂ added shouldprovide a molar ratio of oxygen atoms in the oxygenated hydrocarbons tomoles of hydrogen atoms (i.e., 2 oxygen atoms per molecule of H₂ gas) ofless than or equal to 1.0. For example, where the feedstock is anaqueous solution consisting of glycerol (3 oxygen atoms), the amount ofsupplemental H₂ added to the feedstock is preferably not more than about1.5 moles of H₂ per mole of glycerol (C₃H₈O₃), and preferably not morethan about 1.25, 1.0, 0.75, 0.50 or 0.25. In general, the amount ofsupplemental H₂ added is less than 0.75-times, and more preferably notmore than 0.67, 0.50, 0.33, 0.30, 0.25, 0.20, 0.15, 0.10, 0.05,0.01-times the amount of total H₂ (APR H₂ and external H₂) that wouldprovide a 1:1 atomic ratio of oxygen to hydrogen atoms.

The amount of APR H₂ within a reactor may be identified or detected byany suitable method. APR H₂ may be determined based on the compositionof the product stream as a function of the composition of the feedstockstream, the catalyst composition(s) and the reaction conditions,independent of the actual reaction mechanism occurring within thefeedstock stream. The amount of APR H₂ may be calculated based on thecatalyst, reaction conditions (e.g., flow rate, temperature, pressure,etc.) and the contents of the feedstock and the reaction products. Forexample, the feedstock may be contacted with the APR catalyst (e.g.,platinum) to generate APR H₂ in situ and a first reaction product streamin the absence of a deoxygenation catalyst. The feedstock may also becontacted with both the APR catalyst and the deoxygenation catalyst toproduce a second reaction product stream. By comparing the compositionof the first reaction product stream and the second reaction productstream at comparable reaction conditions, one may identify the presenceof APR H₂ and calculate the amount of APR H₂ produced. For example, anincrease in the amount of oxygenated compounds with greater degrees ofhydrogenation in the reaction product compared to the feedstockcomponents may indicate the presence of APR H₂.

In-Situ Hydrogen Production

One advantage of the process of preparing the component derived from awater-soluble oxygenated hydrocarbon in the present invention is that itallows for the production and use of in-situ generated H₂. The APR H₂ isproduced from the feedstock under aqueous phase reforming conditionsusing an aqueous phase reforming catalyst (APR catalyst). The APRcatalyst is preferably a heterogeneous catalyst capable of catalyzingthe reaction of water and oxygenated hydrocarbons to form H₂ under theconditions described below. In one embodiment, the APR catalyst includesa support and at least one Group VIIIB metal, Fe, Ru, Os, Ir, Co, Rh,Pt, Pd, Ni, alloys and combinations thereof. The APR catalyst may alsoinclude at least one additional material from Group VIIIB, Group VIIB,Group VIB, Group VB, Group IVB, Group IIB, Group IB, Group IVA or GroupVA metals, such as Cu, B, Mn, Re, Cr, Mo, Bi, W, V, Nb, Ta, Ti, Zr, Y,La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, alloys andcombinations thereof. The preferred Group VIIB metal includes Re, Mn, orcombinations thereof. The preferred Group VIB metal includes Cr, Mo, W,or a combination thereof. The preferred Group VIIIB metals include Pt,Rh, Ru, Pd, Ni, or combinations thereof. The supports may include anyone of the catalyst supports described below, depending on the desiredactivity of the catalyst system.

The APR catalyst may also be atomically identical to the deoxygenationcatalyst or the condensation catalyst. For instance, the APR anddeoxygenation catalyst may include Pt alloyed or admixed with Ni, Ru,Cu, Fe, Rh, Re, alloys and combinations thereof. The APR catalyst anddeoxygenation catalyst may also include Ru alloyed or admixed with Ge,Bi, B, Ni, Sn, Cu, Fe, Rh, Pt, alloys and combinations thereof. The APRcatalyst may also include Ni alloyed or admixed with Sn, Ge, Bi, B, Cu,Re, Ru, Fe, alloys and combinations thereof.

Preferred loading of the primary Group VIIIB metal is in the range of0.25 wt % to 25 wt % on carbon, with weight percentages of 0.10% and0.05% increments between, such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%,5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio ofthe second material is in the range of 0.25-to-1 to 10-to-1, includingratios between, such as 0.50, 1.00, 2.50, 5.00, and 7.50-to-1.

A preferred catalyst composition is further achieved by the addition ofoxides of Group IIIB, and associated rare earth oxides. In such event,the preferred components would be oxides of either lanthanum or cerium.The preferred atomic ratio of the Group IIIB compounds to the primaryGroup VIIIB metal is in the range of 0.25-to-1 to 10-to-1, includingratios between, such as 0.50, 1.00, 2.50, 5.00, and 7.50-to-1.

Another preferred catalyst composition is one containing platinum andrhenium. The preferred atomic ratio of Pt to Re is in the range of0.25-to-1 to 10-to-1, including ratios there-between, such as 0.50,1.00, 2.50, 5.00, and 7.00-to-1. The preferred loading of the Pt is inthe range of 0.25 wt % to 5.0 wt %, with weight percentages of 0.10% and0.05% between, such as 0.35%, 0.45%, 0.75%, 1.10%, 1.15%, 2.00%, 2.50%,3.0%, and 4.0%.

Preferably, the APR catalyst and the deoxygenation catalyst are of thesame atomic formulation. The catalysts may also be of differentformulations. In such event, the preferred atomic ratio of the APRcatalyst to the deoxygenation catalyst is in the range of 5:1 to 1:5,such as, without limitation, 4.5:1, 4.0:1, 3.5:1, 3.0:1, 2.5:1, 2.0:1,1.5:1, 1:1, 1:1.5, 1:2.0, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, and anyamounts between.

Similar to the deoxygenation reactions, the temperature and pressureconditions are preferably selected to maintain at least a portion of thefeedstock in the liquid phase at the reactor inlet. The reformingtemperature and pressure conditions may also be selected to morefavorably produce the desired products in the vapor-phase. In general,the APR reaction should be conducted at a temperature where thethermodynamics are favorable. For instance, the minimum pressurerequired to maintain a portion of the feedstock in the liquid phase willvary with the reaction temperature. As temperatures increase, higherpressures will generally be required to maintain the feedstock in theliquid phase. Any pressure above that required to maintain the feedstockin the liquid phase (i.e., vapor-phase) is also a suitable operatingpressure. For vapor phase reactions, the reaction should be conducted ata reforming temperature where the vapor pressure of the oxygenatedhydrocarbon compound is at least about 0.1 atm (and preferably a gooddeal higher), and the thermodynamics of the reaction are favorable. Thetemperature will vary depending upon the specific oxygenated hydrocarboncompound used, but is generally in the range of from about 100° C. to450° C., or from about 100° C. to 300° C., for reactions taking place inthe vapor phase. For liquid phase reactions, the reaction temperaturemay be from about 80° C. to 400° C., and the reaction pressure fromabout 72 psig to 1300 psig.

In one embodiment, the reaction temperature is between about 100° C. and400° C., or between about 120° C. and 300° C., or between about 200° C.and 280° C., or between about 150° C. and 270° C. The reaction pressureis preferably between about 72 and 1300 psig, or between about 72 and1200 psig, or between about 145 and 1200 psig, or between about 200 and725 psig, or between about 365 and 700 psig, or between about 600 and650 psig.

A condensed liquid phase method may also be performed using a modifierthat increases the activity and/or stability of the APR catalyst system.It is preferred that the water and the oxygenated hydrocarbon arereacted at a suitable pH of from about 1.0 to 10.0, or at a pH of fromabout 4.0 to 10.0, including pH value increments of 0.1 and 0.05between. Generally, the modifier is added to the feedstock solution inan amount ranging from about 0.1% to about 10% by weight as compared tothe total weight of the catalyst system used, although amounts outsidethis range are included within the present invention.

Alkali or alkali earth salts may also be added to the feedstock solutionto optimize the proportion of hydrogen in the reaction products.Examples of suitable water-soluble salts include one or more selectedfrom the group consisting of an alkali or an alkali earth metalhydroxide, carbonate, nitrate, or chloride salt. For example, addingalkali (basic) salts to provide a pH of about pH 4.0 to about pH 10.0can improve hydrogen selectivity of reforming reactions.

The addition of acidic compounds may also provide increased selectivityto the desired reaction products in the hydrogenation reactionsdescribed below. It is preferred that the water-soluble acid is selectedfrom the group consisting of nitrate, phosphate, sulfate, chloridesalts, and mixtures thereof. If an acidic modifier is used, it ispreferred that it be present in an amount sufficient to lower the pH ofthe aqueous feed stream to a value between about pH 1.0 and about pH4.0. Lowering the pH of a feed stream in this manner may increase theproportion of oxygenates in the final reaction products.

In general, the reaction should be conducted under conditions where theresidence time of the feedstock solution over the APR catalyst isappropriate to generate an amount of APR hydrogen sufficient to reactwith a second portion of the feedstock solution over the deoxygenationcatalyst to provide the desired oxygenates. For example, the WHSV forthe reaction may be at least about 0.1 gram of oxygenated hydrocarbonper gram of APR catalyst, and preferably between about 1.0 to 40.0 gramsof oxygenated hydrocarbon per gram of APR catalyst, and more preferablybetween about 0.5 to 8.0 grams of oxygenated hydrocarbon per gram of APRcatalyst. In terms of scaled-up production, after start-up, the APRreactor system should be process controlled so that the reactionsproceed at steady-state equilibrium.

Condensation Step

The oxygenates produced are then converted into C₄₊ compounds bycondensation. Without being limited to any specific theories, it isbelieved that the acid condensation reactions generally consist of aseries of steps involving: (a) the dehydration of oxygenates to olefins;(b) oligomerization of the olefins; (c) cracking reactions; (d)cyclization of larger olefins to form aromatics; (e) paraffinisomerization; and (f) hydrogen-transfer reactions to form paraffins.Basic condensation reactions are believed to generally consist of aseries of steps involving: (1) aldol condensation to form aβ-hydroxyketone or β-hydroxyaldehyde; (2) dehydration of theβ-hydroxyketone or β-hydroxyaldehyde to form a conjugated enone; (3)hydrogenation of the conjugated enone to form a ketone or aldehyde,which may participate in further condensation reactions or conversion toan alcohol or hydrocarbon; and (4) hydrogenation of carbonyls toalcohols, or vice-versa. Acid-base condensation reactions are believedto generally involve any of the previous acidic and/or basic reactionssteps.

Production of the C₄₊ compounds occurs by condensation of the oxygenatesin the presence of a condensation catalyst. The condensation catalystwill generally be a catalyst capable of forming longer chain compoundsby linking two oxygen containing species through a new carbon-carbonbond, and converting the resulting compound to a hydrocarbon, alcohol orketone, such as an acid catalyst, basic catalyst or a multi-functionalcatalyst having both acid and base functionality. The condensationcatalyst may include, without limitation, carbides, nitrides, zirconia,alumina, silica, aluminosilicates, phosphates, zeolites, titaniumoxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides,scandium oxides, magnesium oxides, cerium oxides, barium oxides, calciumoxides, hydroxides, heteropolyacids, inorganic acids, acid modifiedresins, base modified resins, and combinations thereof. The condensationcatalyst may include the above alone or in combination with a modifier,such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, andcombinations thereof. The condensation catalyst may also include ametal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd,Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof, toprovide a metal functionality. The condensation catalyst may also beatomically identical to the APR catalyst and/or the deoxygenationcatalyst.

The condensation catalyst may be self-supporting (i.e., the catalystdoes not need another material to serve as a support), or may require aseparate support suitable for suspending the catalyst in the reactantstream. One particularly beneficial support is silica, especially silicahaving a high surface area (greater than 100 square meters per gram),obtained by sol-gel synthesis, precipitation or fuming. In otherembodiments, particularly when the condensation catalyst is a powder,the catalyst system may include a binder to assist in forming thecatalyst into a desirable catalyst shape. Applicable forming processesinclude extrusion, pelletization, oil dropping, or other knownprocesses. Zinc oxide, alumina, and a peptizing agent may also be mixedtogether and extruded to produce a formed material. After drying, thismaterial is calcined at a temperature appropriate for formation of thecatalytically active phase, which usually requires temperatures inexcess of 450° C. Other catalyst supports may include those described infurther detail below.

Acid Catalysts

The acid condensation reaction is performed using acidic catalysts. Theacid catalysts may include, without limitation, aluminosilicates(zeolites), silica-alumina phosphates (SAPO), aluminum phosphates(ALPO), amorphous silica alumina, zirconia, sulfated zirconia,tungstated zirconia, tungsten carbide, molybdenum carbide, titania,acidic alumina, phosphated alumina, phosphated silica, sulfated carbons,phosphated carbons, acidic resins, heteropolyacids, inorganic acids, andcombinations thereof. In one embodiment, the catalyst may also include amodifier, such as Ce, Y, Sc, La, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca,Sr, Ba, and combinations thereof. The catalyst may also be modified bythe addition of a metal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd,Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinationsthereof, to provide metal functionality, and/or sulfides and oxide ofTi, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si,Cu, Zn, Sn, Cd, P, and combinations thereof. Gallium has also been foundto be particularly useful as a promoter for the present process. Theacid catalyst may be homogenous, self-supporting or adhered to any oneof the supports further described below, including supports containingcarbon, silica, alumina, zirconia, titania, vanadia, ceria, nitride,boron nitride, heteropolyacids, alloys and mixtures thereof.

Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, and lanthanides may alsobe exchanged onto zeolites to provide a zeolite catalyst havingactivity. The term “zeolite” as used herein refers not only tomicroporous crystalline aluminosilicate but also for microporouscrystalline metal-containing aluminosilicate structures, such asgalloaluminosilicates and gallosilicates. Metal functionality may beprovided by metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga,In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinationsthereof.

Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12,ZSM-22, ZSM-23, ZSM-35 and ZSM-48. Zeolite ZSM-5, and the conventionalpreparation thereof, is described in U.S. Pat. Nos. 3,702,886; Re.29,948 (highly siliceous ZSM-5); 4,100,262 and 4,139,600, allincorporated herein by reference. Zeolite ZSM-11, and the conventionalpreparation thereof, is described in U.S. Pat. No. 3,709,979, which isalso incorporated herein by reference. Zeolite ZSM-12, and theconventional preparation thereof, is described in U.S. Pat. No.3,832,449, incorporated herein by reference. Zeolite ZSM-23, and theconventional preparation thereof, is described in U.S. Pat. No.4,076,842, incorporated herein by reference. Zeolite ZSM-35, and theconventional preparation thereof, is described in U.S. Pat. No.4,016,245, incorporated herein by reference. Another preparation ofZSM-35 is described in U.S. Pat. No. 4,107,195, the disclosure of whichis incorporated herein by reference. ZSM-48, and the conventionalpreparation thereof, is taught by U.S. Pat. No. 4,375,573, incorporatedherein by reference. Other examples of zeolite catalysts are describedin U.S. Pat. No. 5,019,663 and U.S. Pat. No. 7,022,888, alsoincorporated herein by reference.

As described in U.S. Pat. No. 7,022,888, the acid catalyst may be abifunctional pentasil zeolite catalyst including at least one metallicelement from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga,In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinationsthereof, or a modifier from the group of Ga, In, Zn, Fe, Mo, Au, Ag, Y,Sc, Ni, P, Ta, lanthanides, and combinations thereof. The zeolitepreferably has a strong acidic and dehydrogenation sites, and may beused with reactant streams containing and an oxygenated hydrocarbon at atemperature of below 500° C. The bifunctional pentasil zeolite may haveZSM-5, ZSM-8 or ZSM-11 type crystal structure consisting of a largenumber of 5-membered oxygen-rings, i.e., pentasil rings. The zeolitewith ZSM-5 type structure is a particularly preferred catalyst. Thebifunctional pentasil zeolite catalyst is preferably Ga and/orIn-modified ZSM-5 type zeolites such as Ga and/or In-impregnatedH-ZSM-5, Ga and/or In-exchanged H-ZSM-5, H-gallosilicate of ZSM-5 typestructure and H-galloaluminosilicate of ZSM-5 type structure. Thebifunctional ZSM-5 type pentasil zeolite may contain tetrahedralaluminum and/or gallium present in the zeolite framework or lattice andoctahedral gallium or indium. The octahedral sites are preferably notpresent in the zeolite framework but are present in the zeolite channelsin a close vicinity of the zeolitic protonic acid sites, which areattributed to the presence of tetrahedral aluminum and gallium in thezeolite. The tetrahedral or framework Al and/or Ga is believed to beresponsible for the acid function of zeolite and octahedral ornon-framework Ga and/or In is believed to be responsible for thedehydrogenation function of the zeolite.

In one embodiment, the condensation catalyst may be aH-galloaluminosilicate of ZSM-5 type bifunctional pentasil zeolitehaving framework (tetrahedral) Si/Al and Si/Ga mole ratio of about10-100 and 15-150, respectively, and non-framework (octahedral) Ga ofabout 0.5-5.0 wt. %. When these pentasil H-galloaluminosilicate zeolitesare used as a condensation catalyst, the density of strong acid sitescan be controlled by the framework Al/Si mole ratio: the higher theAl/Si ratio, the higher the density of strong acid sites. The highlydispersed non-framework gallium oxide species can be obtained by thedegalliation of the zeolite by its pre-treatment with H₂ and stream. Thezeolite containing strong acid sites with high density and also highlydispersed non-framework gallium oxide species in close proximity of thezeolite acid site is preferred. The catalyst may optionally contain anybinder such as alumina, silica or clay material. The catalyst can beused in the form of pellets, extrudates and particles of differentshapes and sizes.

The acidic catalysts may include one or more zeolite structurescomprising cage-like structures of silica-alumina. Zeolites arecrystalline microporous materials with well-defined pore structure.Zeolites contain active sites, usually acid sites, which can begenerated in the zeolite framework. The strength and concentration ofthe active sites can be tailored for particular applications. Examplesof suitable zeolites for condensing secondary alcohols and alkanes maycomprise aluminosilicates optionally modified with cations, such as Ga,In, Zn, Mo, and mixtures of such cations, as described, for example, inU.S. Pat. No. 3,702,886, which is incorporated herein by reference. Asrecognized in the art, the structure of the particular zeolite orzeolites may be altered to provide different amounts of varioushydrocarbon species in the product mixture. Depending on the structureof the zeolite catalyst, the product mixture may contain various amountsof aromatic and cyclic hydrocarbons.

Alternatively, solid acid catalysts such as alumina modified withphosphates, chloride, silica, and other acidic oxides could be used inpracticing the present invention. Also, either sulfated zirconia ortungstated zirconia may provide the necessary acidity. Re and Pt/Recatalysts are also useful for promoting condensation of oxygenates toC₅₊ hydrocarbons and/or C₅₊ mono-oxygenates. The Re is sufficientlyacidic to promote acid-catalyzed condensation. Acidity may also be addedto activated carbon by the addition of either sulfates or phosphates.

Base Catalysts

The base condensation reaction is performed using a base catalyst. Thebase catalyst includes at least Li, Na, K, Cs, B, Rb, Mg, Ca, Sr, Si,Ba, Al, Zn, Ce, La, Y, Sc, Y, Zr, Ti, hydrotalcite, zinc-aluminate,phosphate, base-treated aluminosilicate zeolite, a basic resin, basicnitride, alloys or combinations thereof. The base catalyst may alsoinclude an oxide of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In,Co, Ni, Si, Cu, Zn, Sn, Cd, Mg, P, Fe, and combinations thereof. In oneembodiment, the condensation catalyst further includes a metal, such asCu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr,Mo, W, Sn, Os, alloys and combinations thereof. Preferred Group IAmaterials include Li, Na, K, Cs and Rb. Preferred Group IIA materialsinclude Mg, Ca, Sr and Ba. Preferred Group IIB materials include Zn andCd. Preferred Group IIIB materials include Y and La. Basic resinsinclude resins that exhibit basic functionality, such as Amberlyst. Thebase catalyst may be self-supporting or adhered to any one of thesupports further described below, including supports containing carbon,silica, alumina, zirconia, titania, vanadia, ceria, nitride, boronnitride, heteropolyacids, alloys and mixtures thereof.

The base catalyst may also include zeolites and other microporoussupports that contain Group IA compounds, such as Li, Na, K, Cs and Rb.Preferably, the Group IA material is present in an amount greater thanthat required to neutralize the acidic nature of the support. Thesematerials may be used in any combination, and also in combination withalumina or silica. A metal function may also be provided by the additionof group VIIIB metals, or Cu, Ga, In, Zn or Sn.

In one embodiment, the condensation catalyst is derived from thecombination of MgO and Al₂O₃ to form a hydrotalcite material. Anotherpreferred material contains ZnO and Al₂O₃ in the form of a zincaluminate spinel. Yet another preferred material is a combination ofZnO, Al₂O₃, and CuO. Each of these materials may also contain anadditional metal function provided by a Group VIIIB metal, such as Pd orPt. In one embodiment, the base catalyst is a metal oxide containing Cu,Ni, Zn, V, Zr, or mixtures thereof. In another embodiment, the basecatalyst is a zinc aluminate metal containing Pt, Pd Cu, Ni, or mixturesthereof.

Preferred loading of the primary metal is in the range of 0.10 wt % to25 wt %, with weight percentages of 0.10% and 0.05% increments between,such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%, 5.00%, 10.00%, 12.50%, 15.00%and 20.00%. The preferred atomic ratio of the second metal, if any, isin the range of 0.25-to-1 to 10-to-1, including ratios there between,such as 0.50, 1.00, 2.50, 5.00, and 7.50-to-1.

Acid-Base Catalysts

The acid-base condensation reaction is performed using amulti-functional catalyst having both acid and base functionality. Theacid-base catalyst may include hydrotalcite, zinc-aluminate, phosphate,Li, Na, K, Cs, B, Rb, Mg, Si, Ca, Sr, Ba, Al, Ce, La, Sc, Y, Zr, Ti, Zn,Cr, and combinations thereof. In further embodiments, the acid-basecatalyst may also include one or more oxides from the group of Ti, Zr,V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn,Sn, Cd, P, and combinations thereof. The acid-base catalyst may alsoinclude a metal functionality provided by Cu, Ag, Au, Pt, Ni, Fe, Co,Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys orcombinations thereof. In one embodiment, the catalyst further includesZn, Cd or phosphate. In one embodiment, the condensation catalyst is ametal oxide containing Pd, Pt, Cu or Ni, and even more preferably analuminate or zirconium metal oxide containing Mg and Cu, Pt, Pd or Ni.The acid-base catalyst may also include a hydroxyapatite (HAP) combinedwith any one or more of the above metals. The acid-base catalyst may beself-supporting or adhered to any one of the supports further describedbelow, including supports containing carbon, silica, alumina, zirconia,titania, vanadia, ceria, nitride, boron nitride, heteropolyacids, alloysand mixtures thereof.

The condensation catalyst may also include zeolites and othermicroporous supports that contain Group IA compounds, such as Li, NA, K,Cs and Rb. Preferably, the Group IA material is present in an amountless than that required to neutralize the acidic nature of the support.A metal function may also be provided by the addition of group VIIIBmetals, or Cu, Ga, In, Zn or Sn.

In one embodiment, the condensation catalyst is derived from thecombination of MgO and Al₂O₃ to form a hydrotalcite material. Anotherpreferred material contains a combination of MgO and ZrO₂, or acombination of ZnO and Al₂O₃. Each of these materials may also containan additional metal function provided by copper or a Group VIIIB metal,such as Ni, Pd, Pt, or combinations of the foregoing.

If a Group IIB, VIIB, VIIB, VIIIB, IIA or IVA metal is included, theloading of the metal is in the range of 0.10 wt % to 10 wt %, withweight percentages of 0.10% and 0.05% increments between, such as 1.00%,1.10%, 1.15%, 2.00%, 2.50%, 5.00% and 7.50%, etc. If a second metal isincluded, the preferred atomic ratio of the second metal is in the rangeof 0.25-to-1 to 5-to-1, including ratios there between, such as 0.50,1.00, 2.50 and 5.00-to-1.

Condensation Reactions

The specific C₄₊ compounds produced will depend on various factors,including, without limitation, the type of oxygenates in the reactantstream, condensation temperature, condensation pressure, the reactivityof the catalyst, and the flow rate of the reactant stream as it affectsthe space velocity, GHSV and WHSV. Preferably, the reactant stream iscontacted with the condensation catalyst at a WHSV that is appropriateto produce the desired hydrocarbon products. The WHSV is preferably atleast about 0.1 grams of oxygenate in the reactant stream per hour, morepreferably the WHSV is between about 0.1 to 40.0 g/g hr, including aWHSV of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25,30, 35 g/g hr, and increments between.

In general, the condensation reaction should be carried out at atemperature at which the thermodynamics of the proposed reaction arefavorable. For condensed phase liquid reactions, the pressure within thereactor must be sufficient to maintain at least a portion of thereactants in the condensed liquid phase at the reactor inlet. For vaporphase reactions, the reaction should be carried out at a temperaturewhere the vapor pressure of the oxygenates is at least about 0.1 atm(and preferably a good deal higher), and the thermodynamics of thereaction are favorable. The condensation temperature will vary dependingupon the specific oxygenate used, but is generally in the range of fromabout 80° C. to 500° C. for reactions taking place in the vapor phase,and more preferably from about 125° C. to 450° C. For liquid phasereactions, the condensation temperature may be from about 80° C. to 500°C., and the condensation pressure from about 0 psig to 1200 psig.Preferably, the condensation temperature is between about 125° C. and300° C., or between about 125° C. and 250° C., or between about 250° C.and 425° C. The reaction pressure is preferably at least about 0.1 atm,or between about 0 and 1200 psig, or between about 0 and 1000 psig, orbetween about 0 and 700 psig.

Varying the factors above, as well as others, will generally result in amodification to the specific composition and yields of the C₄₊compounds. For example, varying the temperature and/or pressure of thereactor system, or the particular catalyst formulations, may result inthe production of C₄₊ alcohols and/or ketones instead of C₄₊hydrocarbons. The C₄₊ hydrocarbon product may also contain a variety ofolefins, and alkanes of various sizes (typically branched alkanes).Depending upon the condensation catalyst used, the hydrocarbon productmay also include aromatic and cyclic hydrocarbon compounds. The C₄₊hydrocarbon product may also contain undesirably high levels of olefins,which may lead to coking or deposits in combustion engines, or otherundesirable hydrocarbon products. In such event, the hydrocarbonmolecules produced may be optionally hydrogenated to reduce the ketonesto alcohols and hydrocarbons, while the alcohols and unsaturatedhydrocarbon may be reduced to alkanes, thereby forming a more desirablehydrocarbon product having low levels of olefins, aromatics or alcohols.

The finishing step will generally be a hydrogenation reaction thatremoves the remaining carbonyl group or hydroxyl group. In such event,any one of the hydrogenation catalysts described above may be used. Suchcatalysts may include any one or more of the following metals, Cu, Ni,Fe, Co, Ru, Pd, Rh, Pt, Ir, Os, alloys or combinations thereof, alone orwith promoters such as Au, Ag, Cr, Zn, Mn, Sn, Cu, Bi, and alloysthereof, may be used in various loadings ranging from about 0.01 toabout 20 wt % on a support as described above.

In general, the finishing step is carried out at finishing temperaturesof between about 80° C. to 250° C., and finishing pressures in the rangeof about 100 psig to 2000 psig. The finishing step may be conducted inthe vapor phase or liquid phase, and may use in situ generated H₂,external H₂, recycled H₂, or combinations thereof, as necessary.

Other factors, such as the concentration of water or undesiredoxygenates, may also effect the composition and yields of the C₄₊compounds, as well as the activity and stability of the condensationcatalyst. In such event, the process may include a dewatering step thatremoves a portion of the water prior to condensation, or a separationunit for removal of the undesired oxygenates. For instance, a separatorunit, such as a phase separator, extractor, purifier or distillationcolumn, may be installed prior to the condensation step so as to removea portion of the water from the reactant stream containing theoxygenates. A separation unit may also be installed to remove specificoxygenates to allow for the production of a desired product streamcontaining hydrocarbons within a particular carbon range, or for use asend products or in other systems or processes.

C₄₊ Compounds

The practice of the process of preparing the component derived from awater-soluble oxygenated hydrocarbon in the present invention results inthe production of C₄₊ alkanes, C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊cycloalkenes, aryls, fused aryls, C₄₊ alcohols, C₄₊ ketones, andmixtures thereof. The C₄₊ alkanes and C₄₊ alkenes have from 4 to 30carbon atoms (C₄₋₃₀ alkanes and C₄₋₃₀ alkenes) and may be branched orstraight chained alkanes or alkenes. The C₄₊ alkanes and C₄₊ alkenes mayalso include fractions of C₄₋₉, C₇₋₁₄, C₁₂₋₂₄ alkanes and alkenes,respectively, with the C₄₋₉ fraction directed to gasoline, the C₇₋₁₄fraction directed to kerosene (e.g. jet fuels), and the C₁₂₋₂₄ fractiondirected to diesel fuel and other industrial applications. Examples ofvarious C₄₊ alkanes and C₄₊ alkenes include, without limitation, butane,butane, pentane, pentene, 2-methylbutane, hexane, hexane,2-methylpentane, 3-methylpentane, 2,2-dimethylbutane,2,3-dimethylbutane, heptane, heptene, octane, octene,2,2,4,-trimethylpentane, 2,3-dimethyl hexane, 2,3,4-trimethylpentane,2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene,dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene,pentadecane, pentadecene, hexadecane, hexadecane, heptyldecane,heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene,eicosane, eicosene, uneicosane, uneicosene, doeicosane, doeicosene,trieicosane, trieicosene, tetraeicosane, tetraeicosene, and isomersthereof.

The C₅₊ cycloalkanes and C₅₊ cycloalkenes have from 5 to 30 carbon atomsand may be unsubstituted, mono-substituted or multi-substituted. In thecase of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C₃₊ alkyl, a straight chain C₁₊alkyl, a branched C₃₊ alkylene, a straight chain C₁₊ alkylene, astraight chain C₂₊ alkylene, a phenyl or a combination thereof. In oneembodiment, at least one of the substituted groups include a branchedC₃₋₁₂ alkyl, a straight chain C₁₋₁₂ alkyl, a branched C₃₋₁₂ alkylene, astraight chain C₁₋₁₂ alkylene, a straight chain C₂₋₁₂ alkylene, a phenylor a combination thereof. In yet another embodiment, at least one of thesubstituted groups include a branched C₃₋₄ alkyl, a straight chain C₁₋₄alkyl, a branched C₃₋₄ alkylene, straight chain C₁₋₄ alkylene, straightchain C₂₋₄ alkylene, a phenyl or a combination thereof. Examples ofdesirable C₅₊ cycloalkanes and C₅₊ cycloalkenes include, withoutlimitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene,methyl-cyclopentane, methyl-cyclopentene, ethyl-cyclopentane,ethyl-cyclopentene, ethyl-cyclohexane, ethyl-cyclohexene, and isomersthereof.

Aryls will generally consist of an aromatic hydrocarbon in either anunsubstituted (phenyl), mono-substituted or multi-substituted form. Inthe case of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C₃₊ alkyl, a straight chain C₁₊alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene, a phenylor a combination thereof. In one embodiment, at least one of thesubstituted groups include a branched C₃₋₁₂ alkyl, a straight chainC₁₋₁₂ alkyl, a branched C₃₋₁₂ alkylene, a straight chain C₂₋₁₂ alkylene,a phenyl or a combination thereof. In yet another embodiment, at leastone of the substituted groups include a branched C₃₋₄ alkyl, a straightchain C₁₋₄ alkyl, a branched C₃₋₄ alkylene, straight chain C₂₋₄alkylene, a phenyl or a combination thereof. Examples of various arylsinclude, without limitation, benzene, toluene, xylene (dimethylbenzene),ethyl benzene, para xylene, meta xylene, ortho xylene, C₉ aromatics.

Fused aryls will generally consist of bicyclic and polycyclic aromatichydrocarbons, in either an unsubstituted, mono-substituted ormulti-substituted form. In the case of mono-substituted andmulti-substituted compounds, the substituted group may include abranched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene,a straight chain C₂₊ alkylene, a phenyl or a combination thereof. Inanother embodiment, at least one of the substituted groups include abranched C₃₋₄ alkyl, a straight chain C₁₋₄ alkyl, a branched C₃₋₄alkylene, straight chain C₂₋₄ alkylene, a phenyl or a combinationthereof. Examples of various fused aryls include, without limitation,naphthalene, anthracene, tetrahydronaphthalene, anddecahydronaphthalene, indane, indene, and isomers thereof.

The C₄₊ alcohols may also be cyclic, branched or straight chained, andhave from 4 to 30 carbon atoms. In general, the C₄₊ alcohols may be acompound according to the formula R¹—OH, wherein R¹ is a member selectedfrom the group consisting of a branched C₄₊ alkyl, straight chain C₄₊alkyl, a branched C₄₊ alkylene, a straight chain C₄₊ alkylene, asubstituted C₅₊ cycloalkane, an unsubstituted C₅₊ cycloalkane, asubstituted C₅₊ cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl,a phenyl and combinations thereof. Examples of desirable C₄₊ alcoholsinclude, without limitation, butanol, pentanol, hexanol, heptanol,octanol, nonanol, decanol, undecanol, dodecanol, tridecanol,tetradecanol, pentadecanol, hexadecanol, heptyldecanol, octyldecanol,nonyldecanol, eicosanol, uneicosanol, doeicosanol, trieicosanol,tetraeicosanol, and isomers thereof.

The C₄₊ ketones may also be cyclic, branched or straight chained, andhave from 4 to 30 carbon atoms. In general, the C₄₊ ketone may be acompound according to the formula

wherein R³ and R⁴ are independently a member selected from the groupconsisting of a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, abranched C₃₊ alkylene, a straight chain C₂₊ alkylene, a substituted C₅₊cycloalkane, an unsubstituted C₅₊ cycloalkane, a substituted C₅₊cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl, a phenyl and acombination thereof. Examples of desirable C₄₊ ketones include, withoutlimitation, butanone, pentanone, hexanone, heptanone, octanone,nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone,pentadecanone, hexadecanone, heptyldecanone, octyldecanone,nonyldecanone, eicosanone, uneicosanone, doeicosanone, trieicosanone,tetraeicosanone, and isomers thereof.

The lighter fractions of the above, primarily C₄-C₉, may be separatedfor gasoline use. Moderate fractions, such as C₇-C₁₄, may be separatedfor kerosene use (e.g. jet fuel), while heavier fractions, i.e.,C₁₂-C₂₄, may be separated for diesel fuel use. The heaviest fractionsmay be used as lubricants or cracked to produce additional gasolineand/or diesel fractions.

Catalyst Supports

In various embodiments above, the catalyst systems include a supportsuitable for suspending the catalyst in the feedstock solution. Thesupport should be one that provides a stable platform for the chosencatalyst and the reaction conditions. The support may take any formwhich is stable at the chosen reaction conditions to function at thedesired levels, and specifically stable in aqueous feedstock solutions.Such supports include, without limitation, carbon, silica,silica-alumina, alumina, zirconia, titania, ceria, vanadia, nitride,boron nitride, heteropolyacids, hydroxyapatite, zinc oxide, chromia, andmixtures thereof. Nanoporous supports such as zeolites, carbonnanotubes, or carbon fullerene may also be used.

One particularly preferred catalyst support is carbon, especially carbonsupports having relatively high surface areas (greater than 100 squaremeters per gram). Such carbons include activated carbon (granulated,powdered, or pelletized), activated carbon cloth, felts, or fibers,carbon nanotubes or nanohorns, carbon fullerene, high surface areacarbon honeycombs, carbon foams (reticulated carbon foams), and carbonblocks. The carbon may be produced via either chemical or streamactivation of peat, wood, lignite, coal, coconut shells, olive pits, andoil based carbon. Another preferred support is granulated activatedcarbon produced from coconuts. In one embodiment, the APR anddeoxygenation catalyst system consists of Pt on carbon, with the Ptbeing further alloyed or admixed with Ni, Ru, Cu, Fe, Rh, Re, alloys andcombinations thereof.

Another preferred catalyst support is zirconia. The zirconia may beproduced via precipitation of zirconium hydroxide from zirconium salts,through sol-gel processing, or any other method. The zirconia ispreferably present in a crystalline form achieved through calcination ofthe precursor material at temperatures exceeding 400° C. and may includeboth tetragonal and monoclinic crystalline phases. A modifying agent maybe added to improve the textural or catalytic properties of thezirconia. Such modifying agents include, without limitation, sulfate,tungstenate, phosphate, titania, silica, and oxides of Group IIIBmetals, especially Ce, La, or Y. In one embodiment, the APR anddeoxygenation catalyst consists of Pt on a primarily tetragonal phasesilica modified zirconia, with the Pt being further alloyed or admixedwith Ni, Ru, Cu, Fe, Rh, Re, alloys and combinations thereof.

Yet another preferred catalyst support is titania. The titania may beproduced via precipitation from titanium salts, through sol-gelprocessing, or any other method. The titania is preferably present in acrystalline form and may include both anatase and rutile crystallinephases. A modifying agent may be added to improve the textural orcatalytic properties of the titania. Such modifying agents include,without limitation, sulfate, silica, and oxides of Group IIIB metals,especially Ce, La, or Y. In one embodiment, the APR and oxygenateforming catalyst system consists of Ru on a primarily rutile phasetitania, with the Ru being further alloyed or admixed with Ge, Bi, B,Ni, Sn, Cu, Fe, Re, Rh, Pt, alloys and combinations thereof.

Another preferred catalyst support is silica. The silica may beoptionally combined with alumina to form a silica-alumina material. Inone embodiment, the APR catalyst system is Pt on silica-alumina orsilica, with the Pt being further alloyed or admixed with Ni, Ru, Cu,Fe, Rh, Re, alloys and combinations thereof. In another embodiment, theAPR catalyst system is Ni on silica-alumina or silica, with the nickelbeing further alloyed or admixed with Sn, Ge, Bi, Bu, Cu, Re, Ru, Fe,alloys and combinations thereof.

The support may also be treated or modified to enhance its properties.For example, the support may be treated, as by surface-modification, tomodify surface moieties, such as hydrogen and hydroxyl. Surface hydrogenand hydroxyl groups can cause local pH variations that affect catalyticefficiency. The support may also be modified, for example, by treatingit with sulfates, phosphates, tungstenates, silanes, lanthanides, alkalicompounds or alkali earth compounds. For carbon supports, the carbon maybe pretreated with stream, oxygen (from air), inorganic acids orhydrogen peroxide to provide more surface oxygen sites. The preferredpretreatment would be to use either oxygen or hydrogen peroxide. Thepretreated carbon may also be modified by the addition of oxides ofGroup IVB and Group VB. It is preferred to use oxides of Ti, V, Zr andmixtures thereof.

The catalyst systems, whether alone or mixed together, may be preparedusing conventional methods known to those in the art. Such methodsinclude incipient wetting, evaporative impregnation, chemical vapordeposition, wash-coating, magnetron sputtering techniques, and the like.The method chosen to fabricate the catalyst is not particularly criticalto the function of the invention, with the proviso that differentcatalysts will yield different results, depending upon considerationssuch as overall surface area, porosity, etc.

Supplemental Materials

Supplemental materials and compositions (“supplements”) may be added tothe feedstock solution at various stages of the process in order toenhance the reaction or to drive it to the production of the desiredreaction products. Supplements may include, without limitation, acids,salts and additional hydrogen or feedstock. Such supplements may beadded directly to the feedstock stream prior to or contiguous withcontacting the relevant catalyst, or directly to the reaction bed forthe appropriate reactions.

In one embodiment, the supplement may include an additional feedstocksolution for providing additional oxygenated hydrocarbons for oxygenateformation. The feedstock may include any one or more oxygenatedhydrocarbons listed above, including any one or more sugar alcohols,glucose, polyols, glycerol or saccharides. For instance, thesupplemental material may include glycerol. In this embodiment, crudeglycerol is used to initiate the reaction and to produce hydrogen so asto avoid polluting the deoxygenation catalyst with contaminants from thecrude glycerol. Purified glycerol is then added to the feedstocksolution prior to or at the same time the original feedstock solution isplaced in contact with the deoxygenation catalyst to increase theoxygenated hydrocarbons available for processing. It is anticipated thatthe opposite may be employed with the crude glycerol serving as thesupplement depending on the characteristics of the APR catalyst anddeoxygenation catalyst.

In another embodiment, the supplement may include additional oxygenatesfor the condensation reaction. The oxygenates may include any one ormore oxygenates listed above. For instance, the supplemental materialmay include a propyl alcohol. In this embodiment, the propyl alcohol maybe produced in a parallel system from a glycerol feedstock and thencombined with oxygenates produced by the processing of a sorbitolfeedstock in order to provide a reactant stream most effective toproduce a product containing a combination of C₆₋₁₂ hydrocarbons.

In yet another embodiment, the supplemental material may includerecycled oxygenates and/or oxygenated hydrocarbons not fully reactedduring the production process. The oxygenates and oxygenatedhydrocarbons may include any one or more of oxygenates and oxygenatedhydrocarbons listed above.

In still yet another embodiment, the supplemental material may includeacids and salts added to the process. The addition of acidic compoundsmay provide increased selectivity to the desired oxygenates and,ultimately, C₄₊ compounds. Water-soluble acids may include, withoutlimitation, nitrate, phosphate, sulfate, chloride salts, and mixturesthereof. If an optional acidic modifier is used, it is preferred that itbe present in an amount sufficient to lower the pH of the aqueous feedstream to a value between about pH 1.0 and about pH 4.0. Lowering the pHof a feed stream during oxygenate formation in this manner may increasethe proportion of diols, polyols, ketones or alcohols for furthercondensation.

Reactor System

The reactions described herein may be carried out in any reactor ofsuitable design, including continuous-flow, batch, semi-batch ormulti-system reactors, without limitation as to design, size, geometry,flow rates, etc. The reactor system may also use a fluidized catalyticbed system, a swing bed system, fixed bed system, a moving bed system,or a combination of the above. Preferably, the present invention ispracticed utilizing a continuous-flow system at steady-stateequilibrium.

In a continuous flow system, the reactor system includes at least areforming bed adapted to receive an aqueous feedstock solution toproduce hydrogen, a deoxygenation bed adapted to produce oxygenates fromthe hydrogen and a portion of the feedstock solution, and a condensationbed to produce C₄₊ compounds from the oxygenates. The reforming bed isconfigured to contact the aqueous feedstock solution in a vapor phase orliquid phase with the APR catalyst to provide hydrogen in a reactantstream. The deoxygenation bed is configured to receive the reactantstream for contact with the deoxygenation catalyst and production of thedesired oxygenates. The condensation bed is configured to receive thereactant stream for contact with the condensation catalyst andproduction of the desired C₄₊ compounds. For systems not involving anAPR hydrogen production step, the reforming bed may be removed. Forsystems not involving a hydrogen or oxygenate production step, thereforming and deoxygenation beds may be removed. Because the APRcatalyst, deoxygenation catalyst and condensation catalyst may also beatomically identical, the catalysts may exist as the same bed. Forsystems with a hydrogenation or hydrogenolysis step, an additionalreaction bed may be included prior to the deoxygenation and/or reformingbed. For systems with a finishing step, an additional reaction bed forconducting the finishing process may be included after the condensationbed.

In systems producing both hydrogen and oxygenates, the condensation bedmay be positioned within the same reactor vessel along with thereforming bed or in a second reactor vessel in communication with afirst reactor vessel having the reforming bed. The condensation bed maybe within the same reactor vessel along with the reforming ordeoxygenation bed or in a separate reactor vessel in communication withthe reactor vessel having the deoxygenation bed. Each reactor vesselpreferably includes an outlet adapted to remove the product stream fromthe reactor vessel. In systems including a hydrogenation step orhydrogenolysis step, the hydrogenation or hydrogenolysis reaction bedmay be within the same reactor vessel along with the reforming ordeoxygenation bed or in a separate reactor vessel in communication withthe reactor vessel having the reforming bed and/or deoxygenation bed.For systems with a finishing step, the finishing reaction bed may bewithin the same reactor vessel along with the condensation bed or in aseparate reactor vessel in communication with the reactor vessel havingthe condensation bed.

The reactor system may also include additional outlets to allow for theremoval of portions of the reactant stream to further advance or directthe reaction to the desired reaction products, and to allow for thecollection and recycling of reaction byproducts for use in otherportions of the system. The reactor system may also include additionalinlets to allow for the introduction of supplemental materials tofurther advance or direct the reaction to the desired reaction products,and to allow for the recycling of reaction byproducts for use in thereforming process. For example, the system may be designed such thatexcess hydrogen is produced over the APR catalyst, with a portion of theexcess hydrogen removed and reintroduced downstream in the process tosupplement the reaction of the oxygenates over the condensation catalystor the finishing of the condensation product to arrive at the desiredC₄₊ compounds. Alternatively, the system may be designed such thatexcess hydrogen is produced over the APR catalyst, with a portion of theexcess hydrogen removed and used in other upstream processes, such asfeedstock pretreatment processes and hydrogenation or hydrogenolysisreactions.

The reactor system may also include elements which allow for theseparation of the reactant stream into different components which mayfind use in different reaction schemes or to simply promote the desiredreactions. For instance, a separator unit, such as a phase separator,extractor, purifier or distillation column, may be installed prior tothe condensation step to remove water from the reactant stream forpurposes of advancing the condensation reaction to favor the productionof hydrocarbons. A separation unit may also be installed to removespecific oxygenates to allow for the production of a desired productstream containing hydrocarbons within a particular carbon range, or foruse as end products or in other systems or processes.

In one embodiment, the reaction system is configured such that the flowdirection of the aqueous feedstock solution is established to ensuremaximal interaction with the in-situ generated H₂. The reactor may bedesigned so that the reactant stream flows horizontally, vertical ordiagonally to the gravitational plane so as to maximize the efficiencyof the system. In systems where the reactant stream flows vertically ordiagonally to the gravitational plan, the stream may flow either againstgravity (up-flow system), with gravity (down-flow system), or acombination of both. In one preferred embodiment, the APR and/ordeoxygenation reactor vessel is designed as an up-flow system while thecondensation reactor vessel is designed as a down-flow system. In thisembodiment, the feedstock solution first contacts a reforming bedcontaining the APR catalyst to produce in-situ generated H₂. Due to theconfiguration of the reactor, the APR H₂ is then able to, under certainconditions, percolate through a second reaction bed containing thedeoxygenation catalyst at a rate greater than or equal to the feedstocksolution to maximize the interaction of the feedstock solution with theH₂ and deoxygenation catalyst. The resulting reactant stream is thenfeed into the condensation reactor in a down-flow configuration forprocessing.

If the APR catalyst and deoxygenation catalyst are within a singlechamber, the APR catalyst and deoxygenation catalyst may be placed in astacked configuration to allow the feedstock solution to first contactthe APR catalyst and then the deoxygenation catalyst, or a series ofdeoxygenation catalysts depending on the desired reaction products. Thereaction beds for the APR catalyst and deoxygenation catalyst, orcatalysts, may also be placed side-by-side dependent upon the particularflow mechanism employed. In either case, the feedstock solution may beintroduced into the reaction vessel through one or more inlets, and thendirected across the catalysts for processing. In another embodiment, thefeedstock solution is directed across the APR catalyst to produce APRH₂, and then both the APR H₂ and the remaining feedstock solution aredirected across the deoxygenation catalyst, or catalysts, to produce thedesired oxygenates. In a parallel configuration, the feedstock solutionmay be separated to direct a first portion of the feedstock solution tothe reforming bed where APR H₂ is produced, and a second portion to adeoxygenation bed where the desired oxygenates are produced using the insitu generated APR H₂. Alternatively, the reactor may be configured toaccommodate the use of two separate feedstock solutions, with the firstfeedstock solution directed to the APR reactor vessel and the secondfeedstock solution directed to the deoxygenation reactor vessel. In asequential configuration, the reactor may be designed so that thefeedstock solution flows through the APR reactor vessel and into thedeoxygenation reactor vessel. In embodiments employing a combinedAPR/deoxygenation catalyst, the generation of APR H₂ and oxygenatesoccurs simultaneously. In either of these systems, because the APR H₂ isproduced in-situ, the pressure is provided by a pumping mechanism thatalso drives the feedstock solution through the reactor chambers.

FIG. 6 is a process diagram illustrating one potential reactor systemuseful in practicing the process of preparing the component derived froma water-soluble oxygenated hydrocarbon in the present invention. A feedstream of oxygenated hydrocarbons 1 (with or without water) is mixedwith a stream of recycled water and recycled oxygenates at 2 to providean aqueous feedstock solution 3. The feedstock solution 3 is thenhydrogenated in a pretreatment step 4 to provide a feedstock solution 5that is more readily converted to the desired oxygenates. The H₂ for thehydrogenation step may derive from an external source 22 or hydrogenrecycled from the system as illustrated in steps 13-21 below. Thefeedstock solution 5 is reacted in a reactor vessel 8 that contains anAPR catalyst and a deoxygenation catalyst to produce product stream 7containing water, H₂, carbon dioxide, hydrocarbons and oxygenates. Waterin product stream 7 is then removed at 8 to provide a product stream 10containing oxygenates, hydrogen, carbon dioxide and hydrocarbons. Waterfrom dewatering step 8 is then recycled at 9 and 15 for mixing with thestream of oxygenated hydrocarbons at 2. Product stream 10 is then passedthrough reactor vessel 11, which includes a condensation catalyst toproduce product stream 12 containing C₄₊ compounds, water, H₂ and carbondioxide. Product stream 12 is then passed through a three-phaseseparator 13 to separate the non-condensable gases 16 (i.e., hydrogen,carbon dioxide, methane, ethane, and propane) from the hydrocarbonproduct stream 14 containing C₄₊ compounds and water 15. Water 15 fromthe separator can be either recycled or exported from the system. Thenon-condensable gas stream 16 can be passed through a separation unit 17to provide a purified H₂ stream 19 and a raffinate stream 18 containingcarbon dioxide, methane, ethane, propane, and some hydrogen. Thepurified H₂ 19 may then be either exported from the system at 20 orpassed through a recycle compressor 21 to provide recycled hydrogenstream 23.

In another preferred reactor system, illustrated in FIG. 7, a firstreactor system is provided for converting the desired feedstock solutionto C₄₊ compounds. The feedstock solution is stored in tank 1 and thenpassed through feed line 2 into charge pump 3. Charge pump 3 increasesthe pressure of the feedstock solution to the desired reaction pressure,e.g., 600 psi, and then discharges the solution through line 4 into anelectric preheater 5 that heats the feed to the desired inlettemperature. The heated solution 6 is then passed into the process sideof a reactor having essentially a tube-within-tube configuration (tube 7within tube 8). Depending on the pressure of the reactor and thetemperatures at which the several stages are operated, the reactantstream flowing through the reactor tube 7 will generally be maintainedsubstantially in the liquid phase throughout, but may vaporize due tothe heat of the condensation of the distal portion 7 b such that most ofthe product exiting the outlet end of the reactor through line 15 is invapor form.

The stages and stage regions of the reactor tube 7 include anAPR/deoxygenation catalyst (combined) and a condensation catalyst, eachpacked in successive catalytic beds (i.e., one on top of another). Inthis example, reactor tube 7 contains an APR/deoxygenation catalyst inthe proximal portion 7 a of reactor tube 7 and a condensation catalystat the distal portion 7 b. The catalyst system is supported at thebottom with small mesh stainless steel spheres setting on a stainlesssteel frit. Stainless steel spheres are also place on top of thecatalyst bed. To facilitate separation of spent catalyst for recyclingor regeneration, the catalyst beds are separated by means of a porousmaterial, such as glass wool. The reactor may also be physicallyseparated in separate tubes with conduits connecting the tubes to permitcontinuous flow. Such an arrangement may permit better thermalmanagement, allowing optimization of temperature according to therequirements of the reactions in the several reactor stages.

The APR reaction is typically endothermic, while the condensationreaction is typically highly exothermic. Preferably, the reactor systempermits the heat generated in the condensation reaction to be used toheat the APR and deoxygenation reactions. An advantage of conductingboth of these reactions together is that heat is immediately transferredfrom the exothermic condensation reaction to the endothermicreforming/deoxygenation reactions.

The process tube 7 is preferably formed from a heat-conducting materialconfigured to transfer heat from the distal portion 7 b to the proximalportion 7 a. In addition, the process tube may be heated with hot oil orhot air flowing through an annular space between process tube 7 andouter tube 8. The hot air may be generated by heating ambient air from ablower 10 with an electrical heater 12 and sent to the reactor throughline 13. Hot oil may also be used and generated by a heater and pump(not shown) and sent to the reactor through line 13 as well. The flowconfiguration for this system is such that the hot air (or oil) in tube8 flows countercurrent to the process fluid in tube 7. Accordingly, thereactor tube 7 is preferably warmer at the bottom than at the top.

Alternatively, the process tube 7 may be separated into two separatetubes or regions to facilitate the optimization of reaction conditionsseparately for the APR and deoxygenation reactions, and for thecondensation reaction. For example, the separation of spent catalyst forregeneration may be simplified in this manner. In a two-region secondstage in a vertical reactor, heat generated by condensation in the lowerregion may be permitted to move by convection to the upper region foruse in the reformation reaction. The second region may also beconfigured to provide a continuous or step-wise gradient of mixedreformation and condensation catalysts, with more reformation catalystat the upper end and more condensation catalyst at the lower end.

The effluent 15 from reactor tube 7 includes gaseous products (such ashydrogen, CO and CO₂) as well as aqueous and organic liquid products.The effluent is cooled to ambient temperature using a water cooled tubein a tube condenser 16. Effluent 17 from the condenser 16 is thendirected to a three-phase separator to separate the product phases: thenon-condensable gas 18 (upper phase), a lower density organic-liquidphase 19 (middle phase) and a higher-density aqueous-liquid phase 20(lower phase). The system pressure is maintained by controlling the flowof non-condensable gas through line 21. The liquid level is maintainedby controlling the flow of the aqueous-phase components through line 23.The organic-liquid phase is then skimmed off the top of the aqueousphase through line 22.

The aqueous phase 20 is withdrawn through line 23. If the aqueous phase20 contains significant levels of residual oxygenates (i.e., products ofincomplete reformation), the aqueous phase 20 may be conducted throughline 23 back to feed source 6 where it is used for feedstock directedback into the reactor. In this way, the carbon content and energy valueof the intermediate processes are recovered.

The middle phase 19 contains C₅₊ compounds. Typically, this phasecontains hydrocarbons and mono-oxygenates ranging primarily from C₄ toC₃₀. Lighter fractions, primarily C₄-C₉, may be separated for gasolineuse. The moderate fraction, i.e., C₇-C₁₄, may be separated for use askerosene (e.g. in jet fuel). Heavier fractions, i.e., C₁₂-C₂₄, may beseparated for diesel use. The heaviest fractions may be used aslubricants or cracked to produce additional gasoline and/or dieselfractions.

The vapor phase 18 contains hydrogen and other APR reaction products,such as carbon monoxide, carbon dioxide, methane, ethane, propane,butane, pentane, and/or hexane gas. Part of this gas is purged from thesystem to prevent the build-up of light hydrocarbons and CO₂ in thesystem through line 22. The gases may also be used as a fuel source forpurposes of providing heat to the reactor system. In terms of scaled-upproduction, after start-up, the reactor systems could be processcontrolled, and the reactions would proceed at steady-state equilibrium.

Component Having at Least One C_(4+ Compound)

The component having at least one C₄₊ compound derivable from awater-soluble oxygenated hydrocarbon by the process as described aboveis preferably separated into various distillation fractions by any knownmeans before it is used in the liquid fuel compositions of the presentinvention. Preferably, the component having at least one C₄₊ compoundderived from the process as described above is separated into more thanone distillation fraction, wherein at least one of the distillationfractions is a lighter, moderate or heavier fraction described hereinbelow.

As described above, the lighter fractions, primarily C₄-C₉, may beseparated for gasoline use. The moderate fractions, e.g. C₇-C₁₄, may beseparated for use as kerosene, e.g. for jet fuel use. Heavier fractions,e.g. C₁₂-C₂₄, may be separated for diesel fuel use. The heaviestfractions may be used as lubricants or may be cracked to produceadditional fractions for use in gasoline, kerosene and/or dieselfractions.

Because the component having at least one C₄₊ compound derivable from awater-soluble oxygenated hydrocarbon is conveniently derived frombiomass, the age of the component, or fractions thereof, is less than100 years old, preferably less than 40 years old, more preferably lessthan 20 years old, as calculated from the carbon 14 concentration of thecomponent.

Lighter Fractions

The lighter fractions of the component having at least one C₄₊ compoundderivable from a water-soluble oxygenated hydrocarbon preferably has oneor more of the following properties (LF-i to LF-vi):

-   (LF-i) a final boiling point in the range of from 150 to 220° C.,    more preferably in the range of from 160 to 210° C.;-   (LF-ii) a density at 15° C. in the range of from 700 to 890 kg/m³,    more preferably in the range of from 720 to 800 kg/m³;-   (LF-iii) a sulphur content of at most 5 mg/kg, more preferably at    most 1 mg/kg;-   (LF-iv) an oxygen content of at most 3.5% wt., more preferably at    most 3.0% wt., typically at most 2.7% wt.;-   (LF-v) a RON in the range of from 80 to 110, more preferably in the    range of from 90 to 100;-   (LF-vi) a MON in the range of from 70 to 100, more preferably in the    range of from 80 to 90.

Conveniently, the lighter fractions of the component having at least oneC₄₊ compound derivable from a water-soluble oxygenated hydrocarbon hasproperties which accord with each of the properties detailed in LF-i toLF-vi above, more conveniently with each of the preferred values foreach of the properties detailed in LF-i to LF-vi above.

Moderate Fractions

The moderate fractions of the component having at least one C₄₊ compoundderivable from a water-soluble oxygenated hydrocarbon preferably has oneor more of the following properties (MF-i to MF-vix):

-   (MF-i) an initial boiling point in the range of from 120 to 215° C.,    more preferably in the range of from 130 to 205° C.;-   (MF-ii) a final boiling point in the range of from 220 to 320° C.,    more preferably in the range of from 230 to 320° C.;-   (MF-iii) a density at 15° C. in the range of from 700 to 890 kg/m³,    more preferably in the range of from 730 to 840 kg/m³;-   (MF-iv) a sulphur content of at most 0.1% wt., more preferably at    most 0.01% wt.;-   (MF-v) a total aromatics content of at most 30% vol., more    preferably at most 25% vol., even more preferably at most 20% vol.,    most preferably at most 15% vol.;-   (MF-vi) a freeze point of −40° C. or lower, more preferably at least    −47° C. or lower;-   (MF-vii) a smoke point of at least 18 mm, more preferably at least    19 mm, even more preferably at least 25 mm;-   (MF-viii) a viscosity at −20° C. in the range of from 1 to 10 cSt,    more preferably in the range of from 2 to 8 cSt.-   (MF-vix) a specific energy content in the range of from 40 to 47    MJ/kg, more preferably in the range of from 42 to 46 MJ/kg.

Conveniently, the moderate fractions of the component having at leastone C₄₊ compound derivable from a water-soluble oxygenated hydrocarbonhas properties which accord with each of the properties detailed in MF-ito MF-vix above, more conveniently with each of the preferred values foreach of the properties detailed in MF-i to MF-vix above.

Heavier Fractions

The heavier fractions of the component having at least one C₄₊ compoundderivable from a water-soluble oxygenated hydrocarbon preferably has oneor more of the following properties (HF-i to HF-vi):

-   (HF-i) a T95 in the range of from 220 to 380° C., more preferably in    the range of from 260 to 360° C.;-   (HF-ii) a flash point in the range of from 30 to 70° C., more    preferably in the range of from 33 to 60° C.;-   (HF-iii) a density at 15° C. in the range of from 700 to 900 kg/m³,    more preferably in the range of from 750 to 850 kg/m³;-   (HF-iv) a sulphur content of at most 5 mg/kg, more preferably at    most 1 mg/kg;-   (HF-v) an oxygen content of at most 10% wt., more preferably at most    8% wt.;-   (HF-vi) a viscosity at 40° C. in the range of from 0.5 to 6 cSt,    more preferably in the range of from 1 to 5 cSt.

Conveniently, the heavier fractions of the component having at least oneC₄₊ compound derivable from a water-soluble oxygenated hydrocarbon hasproperties which accord with each of the properties detailed in HF-i toHF-vi above, more conveniently with each of the preferred values foreach of the properties detailed in HF-i to HF-vi above.

Liquid Fuel Composition

The amount of the component having at least one C₄₊ compound derivablefrom a water-soluble oxygenated hydrocarbon present in the liquid fuelcomposition of the present invention is at least 0.1% vol., based on theoverall volume of the liquid fuel composition. More preferably, theamount of the component derived from a water-soluble oxygenatedhydrocarbon present in the liquid fuel composition of the presentinvention additionally accords with one or more of the parameters (i) to(xx) listed below:

(i) at least 0.5% vol.(ii) at least 1% vol(iii) at least 1.5% vol(iv) at least 2% vol(v) at least 2.5% vol(vi) at least 3% vol(vii) at least 3.5% vol(viii) at least 4% vol(ix) at least 4.5% vol(x) at least 5% vol(xi) at most 99.5% vol.(xii) at most 99% vol.(xiii) at most 98% vol.(xiv) at most 97% vol.(xv) at most 96% vol.(xvi) at most 95% vol.(xvii) at most 90% vol.(xviii) at most 85% vol.(xix) at most 80% vol.(xx) at most 75% vol.

Conveniently, the amount of the component having at least one C₄₊compound derivable from a water-soluble oxygenated hydrocarbon presentin the liquid fuel composition of the present invention accords with oneparameter selected from (i) to (x) above, and one parameter selectedfrom (xi) to (xx) above.

Conveniently, for gasoline compositions according to the presentinvention, the amount of the component having at least one C₄₊ compoundderivable from a water-soluble oxygenated hydrocarbon present in thegasoline composition will be in the range of from 0.1 to 60% vol, 0.5 to55% vol or 1 to 50% vol.

Conveniently, for diesel fuel compositions according to the presentinvention, the amount of the component having at least one C₄₊ compoundderivable from a water-soluble oxygenated hydrocarbon present in thediesel fuel composition will be in the range of from 0.1 to 60% vol, 0.5to 55% vol or 1 to 50% vol.

Conveniently, for kerosene compositions according to the presentinvention, the amount of the component having at least one C₄₊ compoundderivable from a water-soluble oxygenated hydrocarbon present in thekerosene composition will be in the range of from 0.1 to 90% vol, 0.5 to85% vol or 1 to 80% vol, such as in the range of from 0.1 to 60% vol,0.5 to 55% vol or 1 to 50% vol.

The liquid fuel composition comprising of the present invention istypically selected from a gasoline, kerosene or diesel fuel composition.

If the liquid fuel composition is a gasoline composition, then thegasoline composition has an initial boiling point in the range of from15° C. to 70° C. (IP123), a final boiling point of at most 230° C.(IP123), a RON in the range of from 85 to 110 (ASTM D2699) and a MON inthe range of from 75 to 100 (ASTM D2700).

If the liquid fuel composition is a kerosene composition, then thekerosene composition has an initial boiling point in the range of from110 to 150° C., a final boiling point in the range of from 200 to 320°C. and a viscosity at −20° C. in the range of from 0.8 to 10 mm²/s (ASTMD445).

If the liquid fuel composition is a diesel fuel composition, then thediesel fuel composition has an initial boiling point in the range offrom 130° C. to 230° C. (IP123), a final boiling point of at most 410°C. (IP123) and a cetane number in the range of from 35 to 120 (ASTMD613).

Preferably, the liquid fuel composition of the present inventionadditionally comprises one or more fuel additive.

Gasoline Compositions

The gasoline composition according to the present invention typicallycomprise mixtures of hydrocarbons boiling in the range from 15 to 230°C., more typically in the range of from 25 to 230° C. (EN-ISO 3405). Theinitial boiling point of the gasoline compositions according to thepresent invention are in the range of from 15 to 70° C. (IP123),preferably in the range of from 20 to 60° C., more preferably in therange of from 25 to 50° C. The final boiling point of the gasolinecompositions according to the present invention is at most 230° C.,preferably at most 220° C., more preferably at most 210° C. The optimalranges and distillation curves typically varying according to climateand season of the year.

In addition to the component having at least one C₄₊ compound derivablefrom a water-soluble oxygenated hydrocarbon, the hydrocarbons in thegasoline composition may be derived by any means known in the art,conveniently the hydrocarbons may be derived in any known manner fromstraight-run gasoline, synthetically-produced aromatic hydrocarbonmixtures, thermally or catalytically cracked hydrocarbons, hydro-crackedpetroleum fractions, catalytically reformed hydrocarbons or mixtures ofthese.

The research octane number (RON) of the gasoline compositions accordingto the present invention is in the range of from 85 to 110 (ASTM D2699).Preferably, the RON of the gasoline composition will be at least 90, forinstance in the range of from 90 to 110, more preferably at least 91,for instance in the range of from 91 to 105, even more preferably atleast 92, for instance in the range of from 92 to 103, even morepreferably at least 93, for instance in the range of from 93 to 102, andmost preferably at least 94, for instance in the range of from 94 to100.

The motor octane number (MON) of the gasoline compositions according tothe present invention is in the range of from 75 to 100 (ASTM D2699).Preferably, the MON of the gasoline composition will be at least 80, forinstance in the range of from 80 to 100, more preferably at least 81,for instance in the range of from 81 to 95, even more preferably atleast 82, for instance in the range of from 82 to 93, even morepreferably at least 83, for instance in the range of from 83 to 92, andmost preferably at least 84, for instance in the range of from 84 to 90.

Typically, gasoline compositions comprise a mixture of componentsselected from one or more of the following groups; saturatedhydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, andoxygenated hydrocarbons. Conveniently, the gasoline composition maycomprise a mixture of saturated hydrocarbons, olefinic hydrocarbons,aromatic hydrocarbons, and, optionally, oxygenated hydrocarbons.

Typically, the olefinic hydrocarbon content of the gasoline compositionis in the range of from 0 to 40 percent by volume based on the gasoline(ASTM D1319); preferably, the olefinic hydrocarbon content of thegasoline composition is in the range of from 0 to 30 percent by volumebased on the gasoline composition, more preferably, the olefinichydrocarbon content of the gasoline composition is in the range of from0 to 20 percent by volume based on the gasoline composition.

Typically, the aromatic hydrocarbon content of the gasoline compositionis in the range of from 0 to 70 percent by volume based on the gasoline(ASTM D1319), for instance the aromatic hydrocarbon content of thegasoline composition is in the range of from 10 to 60 percent by volumebased on the gasoline composition; preferably, the aromatic hydrocarboncontent of the gasoline composition is in the range of from 0 to 50percent by volume based on the gasoline composition, for instance thearomatic hydrocarbon content of the gasoline composition is in the rangeof from 10 to 50 percent by volume based on the gasoline composition.

The benzene content of the gasoline composition is at most 10 percent byvolume, more preferably at most 5 percent by volume, especially at most1 percent by volume based on the gasoline composition.

The gasoline composition preferably has a low or ultra low sulphurcontent, for instance at most 1000 ppmw (parts per million by weight),preferably no more than 500 ppmw, more preferably no more than 100, evenmore preferably no more than 50 and most preferably no more than even 10ppmw.

The gasoline composition also preferably has a low total lead content,such as at most 0.005 g/l, most preferably being lead free—having nolead compounds added thereto (i.e. unleaded).

When the gasoline composition comprises oxygenated hydrocarbons, atleast a portion of non-oxygenated hydrocarbons will be substituted foroxygenated hydrocarbons. The oxygen content of the gasoline may be up to30 percent by weight (EN 1601) based on the gasoline composition. Forexample, the oxygen content of the gasoline may be up to 25 percent byweight, preferably up to 10 percent by weight. Conveniently, theoxygenate concentration will have a minimum concentration selected fromany one of 0, 0.2, 0.4, 0.6, 0.8, 1.0, and 1.2 percent by weight, and amaximum concentration selected from any one of 5, 4.5, 4.0, 3.5, 3.0,and 2.7 percent by weight.

Examples of oxygenated hydrocarbons, other than the oxygenatedhydrocarbons that may be present in the component having at least oneC₄₊ compound derivable from a water-soluble oxygenated hydrocarbon, thatmay be incorporated into the gasoline include alcohols, ethers, esters,ketones, aldehydes, carboxylic acids and their derivatives, and oxygencontaining heterocyclic compounds. Preferably, the oxygenatedhydrocarbons that may be incorporated into the gasoline are selectedfrom alcohols (such as methanol, ethanol, propanol, iso-propanol,butanol, tert-butanol and iso-butanol), ethers (preferably etherscontaining 5 or more carbon atoms per molecule, e.g., methyl tert-butylether) and esters (preferably esters containing 5 or more carbon atomsper molecule); a particularly preferred oxygenated hydrocarbon isethanol.

When oxygenated hydrocarbons are present in the gasoline composition,the amount of oxygenated hydrocarbons in the gasoline composition mayvary over a wide range. For example, gasolines comprising a majorproportion of oxygenated hydrocarbons are currently commerciallyavailable in countries such as Brazil and U.S.A, e.g. E85, as well asgasolines comprising a minor proportion of oxygenated hydrocarbons, e.g.E10 and E5. Therefore, the amount of oxygenated hydrocarbons present inthe gasoline composition is preferably selected from one of thefollowing amounts: up to 85 percent by volume; up to 65 percent byvolume; up to 30 percent by volume; up to 20 percent by volume; up to 15percent by volume; and, up to 10 percent by volume, depending upon thedesired final formulation of the gasoline. Conveniently, the gasolinecomposition may contain at least 0.5, 1.0 or 2.0 percent by volumeoxygenated hydrocarbons.

Examples of suitable gasoline compositions include gasolines which havean olefinic hydrocarbon content of from 0 to 20 percent by volume (ASTMD1319), an oxygen content of from 0 to 5 percent by weight (EN 1601), anaromatic hydrocarbon content of from 0 to 50 percent by volume (ASTMD1319) and a benzene content of at most 1 percent by volume.

Whilst not critical to the present invention, the gasoline compositionsof the present invention may conveniently additionally include one ormore fuel additive. The concentration and nature of the fuel additive(s)that may be included in the gasoline composition of the presentinvention is not critical. Non-limiting examples of suitable types offuel additives that can be included in the gasoline composition of thepresent invention include anti-oxidants, corrosion inhibitors,detergents, dehazers, antiknock additives, metal deactivators,valve-seat recession protectant compounds, dyes, friction modifiers,carrier fluids, diluents and markers. Examples of suitable suchadditives are described generally in U.S. Pat. No. 5,855,629.

Conveniently, the fuel additives can be blended with one or morediluents or carrier fluids, to form an additive concentrate, theadditive concentrate can then be admixed with the gasoline compositionof the present invention.

The (active matter) concentration of any additives present in thegasoline composition of the present invention is preferably up to 1percent by weight, more preferably in the range from 5 to 1000 ppmw,advantageously in the range of from 75 to 300 ppmw, such as from 95 to150 ppmw.

Alternatively, the gasoline composition of the present invention may bean aviation gasoline. If the gasoline composition is an aviationgasoline then, depending upon the grade of the aviation gasoline, theLean Mixture Motor Octane Number will be at least 80 (ASTM D2700) andthe Rich Mixture Octane Number will be at least 87 (ASTM D 909), or theLean Mixture Motor Octane Number will be at least 99.5 (ASTM D2700) andthe Performance Number will be at least 130 (ASTM D 909). Furthermore,if the gasoline composition is an aviation gasoline then the Reid VapourPressure at 37.8° C. will be in the range of from 38.0 to 49.0 kPa (ASTMD323), the final boiling point will be at most 170° C. (ASTM D 86), andthe tetraethyl lead content will be at most 0.85 gPb/l.

Kerosene Fuel Compositions

The kerosene fuel compositions of the present invention have use inaviation engines, such as jet engines or aero diesel engines, but alsoin any other suitable power or lighting source.

In addition to the component having at least one C₄₊ compound derivablefrom a water-soluble oxygenated hydrocarbon, the kerosene fuelcomposition may comprise a mixture of two or more different fuelcomponents, and/or be additivated as described below.

The kerosene fuel compositions will typically have boiling points withinthe range of 80 to 320° C., preferably in the range of 110 to 320° C.,more preferably in the range of from 130 to 300° C., depending on gradeand use. They will typically have a density from 775 to 845 kg/m³,preferably from 780 to 830 kg/m³, at 15° C. (e.g. ASTM D4502 or IP 365).They will typically have an initial boiling point in the range 80 to150° C., preferably in the range 110 to 150° C., and a final boilingpoint in the range 200 to 320° C. Their kinematic viscosity at −20° C.(ASTM D445) is typically in the range of from 0.8 to 10 mm²/s,preferably from 1.2 to 8.0 mm²/s.

It may be desirable for the kerosene fuel composition to contain aFischer-Tropsch derived fuel, if the kerosene fuel composition doescontain a Fischer-Tropsch derived fuel, then it will convenientlycontain 5% v or greater, preferably 10% v or greater, or more preferably25% v or greater, of a Fischer-Tropsch derived fuel.

The Fischer-Tropsch derived fuel should be suitable for use as akerosene fuel. Its components (or the majority, for instance 95% w orgreater, thereof) should therefore have boiling points within the rangegiven above, i.e. from 110 to 320° C., preferably from 130 to 300° C. Itwill suitably have a 90% v/v distillation temperature (T90) of from 180to 250° C., preferably 180 to 230° C.

By “Fischer-Tropsch derived” is meant that the fuel is, or derives from,a synthesis product of a Fischer-Tropsch condensation process. TheFischer-Tropsch reaction converts carbon monoxide and hydrogen intolonger chain, usually paraffinic, hydrocarbons:

n(CO+2H₂)═(—CH₂—)_(n) +nH₂O+heat,

in the presence of an appropriate catalyst and typically at elevatedtemperatures (e.g. 125 to 300° C., preferably 175 to 250° C.) and/orpressures (e.g. 500 to 10000 kPa, preferably 1200 to 5000 kPa).Hydrogen:carbon monoxide ratios other than 2:1 may be used if desired.

The carbon monoxide and hydrogen may themselves be derived from organicor inorganic, natural or synthetic sources, typically either fromnatural gas or from organically derived methane.

A kerosene product may be obtained directly from this reaction, orindirectly for instance by fractionation of a Fischer-Tropsch synthesisproduct or from a hydrotreated Fischer-Tropsch synthesis product.Hydrotreatment can involve hydrocracking to adjust the boiling range(see, e.g. GB-B-2077289 and EP-A-0147873) and/or hydroisomerisationwhich can improve base fuel cold flow properties by increasing theproportion of branched paraffins. EP-A-0583836 describes a two-stephydrotreatment process in which a Fischer-Tropsch synthesis product isfirstly subjected to hydroconversion under conditions such that itundergoes substantially no isomerisation or hydrocracking (thishydrogenates the olefinic and oxygen-containing components), and then atleast part of the resultant product is hydroconverted under conditionssuch that hydrocracking and isomerisation occur to yield a substantiallyparaffinic hydrocarbon fuel. The desired kerosene fraction(s) maysubsequently be isolated for instance by distillation.

Other post-synthesis treatments, such as polymerisation, alkylation,distillation, cracking-decarboxylation, isomerisation andhydroreforming, may be used to modify the properties of Fischer-Tropschcondensation products, as described for example in U.S. Pat. No.4,125,566 and U.S. Pat. No. 4,478,955.

Typical catalysts for the Fischer-Tropsch synthesis of paraffinichydrocarbons comprise, as the catalytically active component, a metalfrom Group VIII of the periodic table, in particular ruthenium, iron,cobalt or nickel. Suitable such catalysts are described for example inEP-A-0583836 (pages 3 and 4).

An example of a Fischer-Tropsch based process is the SMDS (Shell MiddleDistillate Synthesis) described in “The Shell Middle DistillateSynthesis Process”, van der Burgt et al (paper delivered at the 5^(th)Synfuels Worldwide Symposium, Washington D.C., November 1985; see alsothe November 1989 publication of the same title from Shell InternationalPetroleum Company Ltd., London, UK). This process (also sometimesreferred to as the Shell™ “Gas-to-Liquids” or “GTL” technology) producesmiddle distillate range products by conversion of a natural gas(primarily methane) derived synthesis gas into a heavy long-chainhydrocarbon (paraffin) wax which can then be hydroconverted andfractionated to produce liquid transport fuels such as kerosene fuelcompositions. A version of the SMDS process, using a fixed-bed reactorfor the catalytic conversion step, is currently in use in Bintulu,Malaysia and its products have been blended with petroleum derived gasoils in commercially available automotive fuels.

Gas oils and kerosenes prepared by the SMDS process are commerciallyavailable from the Royal Dutch/Shell Group of Companies.

Suitably, in accordance with the present invention, the Fischer-Tropschderived kerosene fuel will consist of at least 90% w, preferably atleast 95% w, more preferably at least 98% w, even more preferably atleast 99% w, most preferably at least 99.8% w, of paraffinic components,typically normal and iso-paraffins. The weight ratio of normal toiso-paraffins will preferably be in the ranges indicated above. Theactual value for this ratio will be determined, in part, by thehydroconversion process used to prepare the kerosene from theFischer-Tropsch synthesis product. Some cyclic paraffins may also bepresent.

By virtue of the Fischer-Tropsch process, a Fischer-Tropsch derivedkerosene has essentially no, or undetectable levels of, sulphur andnitrogen. Compounds containing these heteroatoms tend to act as poisonsfor Fischer-Tropsch catalysts and are therefore removed from thesynthesis gas feed. Further, the process as usually operated produces noor virtually no aromatic components. The aromatics content of aFischer-Tropsch kerosene, as determined by ASTM D4629, will typically bebelow 5% w, preferably below 2% w, more preferably below 1% w and mostpreferably below 0.2% w.

The Fischer-Tropsch derived kerosene which may be used in the kerosenefuel compositions of the present invention will typically have a densityfrom 730 to 770 kg/m³ at 15° C.; a kinematic viscosity from 1.2 to 6,preferably from 2 to 5, more preferably from 2 to 3.5, mm²/s at −20° C.;and a sulphur content of 20 ppmw (parts per million by weight) or less,preferably of 5 ppmw or less.

Preferably it is a product prepared by a Fischer-Tropsch methanecondensation reaction using a hydrogen/carbon monoxide ratio of lessthan 2.5, preferably less than 1.75, more preferably from 0.4 to 1.5,and ideally using a cobalt containing catalyst. Suitably it will havebeen obtained from a hydrocracked Fischer-Tropsch synthesis product (forinstance as described in GB-B-2077289 and/or EP-A-0147873), or morepreferably a product from a two-stage hydroconversion process such asthat described in EP-A-0583836 (see above). In the latter case,preferred features of the hydroconversion process may be as disclosed atpages 4 to 6, and in the examples, of EP-A-0583836.

The kerosene fuel composition of the present invention preferablycontains no more than 3000 ppmw sulphur, more preferably no more than2000 ppmw, or no more than 1000 ppmw, or no more than 500 ppmw sulphur.

The kerosene fuel composition or the components thereof may beadditivated (additive-containing) or unadditivated (additive-free). Ifadditivated, e.g. at the refinery or in later stages of fueldistribution, it will contain minor amounts of one or more additivesselected for example from anti-static agents (e.g. STADIS™ 450 (ex.Octel)), antioxidants (e.g. substituted tertiary butyl phenols), metaldeactivator additives (e.g. N,N′-disalicylidene 1,2-propanediamine),fuel system icing inhibitor additives (e.g. diethylene glycol monomethylether), corrosion inhibitor/lubricity improver additives (e.g. APOLLO™PRI 19 (ex. Apollo), DCI 4A (ex. Octel), NALCO™ 5403 (ex. Nalco)), orthermal stability improving additives (e.g. APA 101™, (ex. Shell)) thatare approved in international civil and/or military jet fuelspecifications.

Unless otherwise stated, the (active matter) concentration of each suchadditional component in the additivated kerosene fuel composition is atlevels required or allowed in international jet fuel specifications.

In the above, amounts (concentrations, % v, ppmw, wt %) of componentsare of active matter, i.e. exclusive of volatile solvents/diluentmaterials, unless otherwise stipulated in the relevant specification.

The kerosene fuel composition of the present invention is particularlyapplicable where the kerosene fuel composition is used or intended to beused in a jet engine.

Diesel Fuel Compositions

The diesel fuel composition according to the present invention typicallycomprise mixtures of hydrocarbons boiling in the range from 130 to 410°C., more typically in the range of from 150 to 400° C. The initialboiling point of the diesel fuel compositions according to the presentinvention are in the range of from 130 to 230° C. (IP123), preferably inthe range of from 140 to 220° C., more preferably in the range of from150 to 210° C. The final boiling point of the diesel fuel compositionsaccording to the present invention is at most 410° C., preferably atmost 405° C., more preferably at most 400° C.

In addition to the component having at least one C₄₊ compound derivablefrom a water-soluble oxygenated hydrocarbon, the diesel fuel compositionmay comprise a mixture of two or more different diesel fuel components,and/or be additivated as described below.

Such diesel fuel compositions will contain one or more base fuels whichmay typically comprise liquid hydrocarbon middle distillate gas oil(s),for instance petroleum derived gas oils. Such fuels will typically haveboiling points within the range described above, depending on grade anduse. They will typically have a density from 750 to 1000 kg/m³,preferably from 780 to 860 kg/m³, at 15° C. (e.g. ASTM D4502 or IP 365)and a cetane number (ASTM D613) of from 35 to 120, more preferably from40 to 85. They will typically have an initial boiling point in the rangedescribed above and a final boiling point of at most 410° C., preferablyat most 405° C., more preferably at most 400° C., most preferably in therange 290 to 400° C. Their kinematic viscosity at 40° C. (ASTM D445)might suitably be from 1.2 to 4.5 mm²/s.

An example of a petroleum derived gas oil is a Swedish Class 1 basefuel, which will have a density from 800 to 820 kg/m³ at 15° C. (SS-ENISO 3675, SS-EN ISO 12185), a T95 of 320° C. or less (SS-EN ISO 3405)and a kinematic viscosity at 40° C. (SS-EN ISO 3104) from 1.4 to 4.0mm²/s, as defined by the Swedish national specification EC1.

Optionally, non-mineral oil based fuels, such as biofuels (other thanthe component having at least one C₄₊ compound derivable from awater-soluble oxygenated hydrocarbon) or Fischer-Tropsch derived fuels,may also form or be present in the diesel fuel. Such Fischer-Tropschfuels may for example be derived from natural gas, natural gas liquids,petroleum or shale oil, petroleum or shale oil processing residues, coalor biomass.

The amount of Fischer-Tropsch derived fuel used in the diesel fuelcomposition of the present invention may be from 0% to the remainingportion of the diesel fuel composition (i.e. the portion of the dieselfuel composition that is not the component having at least one C₄₊compound derivable from a water-soluble oxygenated hydrocarbon),preferably from 5% to the remaining portion of the diesel fuelcomposition, more preferably from 5% to 75% v of the diesel fuelcomposition. It may be desirable for such a diesel fuel composition tocontain 10% v or greater, more preferably 20% v or greater, still morepreferably 30% v or greater, of the Fischer-Tropsch derived fuel. It isparticularly preferred for such diesel fuels to contain 30 to 75% v, andparticularly 30 or 70% v, of the Fischer-Tropsch derived fuel. Thebalance of the diesel fuel is made up of the component having at leastone C₄₊ compound derivable from a water-soluble oxygenated hydrocarbonand optionally one or more other diesel fuel components.

Such a Fischer-Tropsch derived fuel component is any fraction of themiddle distillate fuel range, which can be isolated from the (optionallyhydrocracked) Fischer-Tropsch synthesis product. Typical fractions willboil in the naphtha, kerosene or gas oil range. Preferably, aFischer-Tropsch product boiling in the kerosene or gas oil range is usedbecause these products are easier to handle in for example domesticenvironments. Such products will suitably comprise a fraction largerthan 90 wt % which boils between 160 and 400° C., preferably to about370° C. Examples of Fischer-Tropsch derived kerosene and gas oils aredescribed in EP-A-0583836, WO-A-97/14768, WO-A-97/14769, WO-A-00/11116,WO-A-00/11117, WO-A-01/83406, WO-A-01/83648, WO-A-01/83647,WO-A-01/83641, WO-A-00/20535, WO-A-00/20534, EP-A-1101813, U.S. Pat. No.5,766,274, U.S. Pat. No. 5,378,348, U.S. Pat. No. 5,888,376 and U.S.Pat. No. 6,204,426.

The Fischer-Tropsch product will suitably contain more than 80 wt % andmore suitably more than 95 wt % iso and normal paraffins and less than 1wt % aromatics, the balance being naphthenics compounds. The content ofsulphur and nitrogen will be very low and normally below the detectionlimits for such compounds. For this reason the sulphur content of adiesel fuel composition containing a Fischer-Tropsch product may be verylow.

The diesel fuel composition preferably contains no more than 5000 ppmwsulphur, more preferably no more than 500 ppmw, or no more than 350ppmw, or no more than 150 ppmw, or no more than 100 ppmw, or no morethan 70 ppmw, or no more than 50 ppmw, or no more than 30 ppmw, or nomore than 20 ppmw, or most preferably no more than 15 ppmw sulphur.

The diesel fuel typically also includes one or more fuel additive.

The diesel base fuel may itself be additivated (additive-containing) orunadditivated (additive-free). If additivated, e.g. at the refinery, itwill contain minor amounts of one or more additives selected for examplefrom anti-static agents, pipeline drag reducers, flow improvers (e.g.ethylene/vinyl acetate copolymers or acrylate/maleic anhydridecopolymers), lubricity additives, antioxidants and wax anti-settlingagents.

Detergent-containing diesel fuel additives are known and commerciallyavailable. Such additives may be added to diesel fuels at levelsintended to reduce, remove, or slow the build up of engine deposits.

Examples of detergents suitable for use in diesel fuel additives for thepresent purpose include polyolefin substituted succinimides orsuccinamides of polyamines, for instance polyisobutylene succinimides orpolyisobutylene amine succinamides, aliphatic amines, Mannich bases oramines and polyolefin (e.g. polyisobutylene) maleic anhydrides.Succinimide dispersant additives are described for example inGB-A-960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A-0557516 andWO-A-98/42808. Particularly preferred are polyolefin substitutedsuccinimides such as polyisobutylene succinimides.

The diesel fuel additive mixture may contain other components inaddition to the detergent. Examples are lubricity enhancers; dehazers,e.g. alkoxylated phenol formaldehyde polymers; anti-foaming agents (e.g.polyether-modified polysiloxanes); ignition improvers (cetane improvers)(e.g. 2-ethylhexyl nitrate (EHN), cyclohexyl nitrate, di-tert-butylperoxide and those disclosed in U.S. Pat. No. 4,208,190 at column 2,line 27 to column 3, line 21); anti-rust agents (e.g. a propane-1,2-diolsemi-ester of tetrapropenyl succinic acid, or polyhydric alcohol estersof a succinic acid derivative, the succinic acid derivative having on atleast one of its alpha-carbon atoms an unsubstituted or substitutedaliphatic hydrocarbon group containing from 20 to 500 carbon atoms, e.g.the pentaerythritol diester of polyisobutylene-substituted succinicacid); corrosion inhibitors; reodorants; anti-wear additives;anti-oxidants (e.g. phenolics such as 2,6-di-tert-butylphenol, orphenylenediamines such as N,N′-di-sec-butyl-p-phenylenediamine); metaldeactivators; combustion improvers; static dissipator additives; coldflow improvers; and wax anti-settling agents.

The diesel fuel additive mixture may contain a lubricity enhancer,especially when the diesel fuel composition has a low (e.g. 500 ppmw orless) sulphur content. In the additivated diesel fuel composition, thelubricity enhancer is conveniently present at a concentration of lessthan 1000 ppmw, preferably between 50 and 1000 ppmw, more preferablybetween 70 and 1000 ppmw. Suitable commercially available lubricityenhancers include ester- and acid-based additives. Other lubricityenhancers are described in the patent literature, in particular inconnection with their use in low sulphur content diesel fuels, forexample in:

-   -   the paper by Danping Wei and H. A. Spikes, “The Lubricity of        Diesel Fuels”, Wear, III (1986) 217-235;    -   WO-A-95/33805—cold flow improvers to enhance lubricity of low        sulphur fuels;    -   WO-A-94/17160—certain esters of a carboxylic acid and an alcohol        wherein the acid has from 2 to 50 carbon atoms and the alcohol        has 1 or more carbon atoms, particularly glycerol monooleate and        di-isodecyl adipate, as fuel additives for wear reduction in a        diesel engine injection system;    -   U.S. Pat. No. 5,490,864—certain dithiophosphoric        diester-dialcohols as anti-wear lubricity additives for low        sulphur diesel fuels; and    -   WO-A-98/01516—certain alkyl aromatic compounds having at least        one carboxyl group attached to their aromatic nuclei, to confer        anti-wear lubricity effects particularly in low sulphur diesel        fuels.

It may also be preferred for the diesel fuel composition to contain ananti-foaming agent, more preferably in combination with an anti-rustagent and/or a corrosion inhibitor and/or a lubricity enhancingadditive.

Unless otherwise stated, the (active matter) concentration of each suchadditive component in the additivated diesel fuel composition ispreferably up to 10000 ppmw, more preferably in the range from 0.1 to1000 ppmw, advantageously from 0.1 to 300 ppmw, such as from 0.1 to 150ppmw.

The (active matter) concentration of any dehazer in the diesel fuelcomposition will preferably be in the range from 0.1 to 20 ppmw, morepreferably from 1 to 15 ppmw, still more preferably from 1 to 10 ppmw,advantageously from 1 to 5 ppmw. The (active matter) concentration ofany ignition improver present will preferably be 2600 ppmw or less, morepreferably 2000 ppmw or less, conveniently from 300 to 1500 ppmw. The(active matter) concentration of any detergent in the diesel fuelcomposition will preferably be in the range from 5 to 1500 ppmw, morepreferably from 10 to 750 ppmw, most preferably from 20 to 500 ppmw.

In the case of a diesel fuel composition, for example, the fuel additivemixture will typically contain a detergent, optionally together withother components as described above, and a diesel fuel-compatiblediluent, which may be a mineral oil, a solvent such as those sold byShell companies under the trade mark “SHELLSOL”, a polar solvent such asan ester and, in particular, an alcohol, e.g. hexanol, 2-ethylhexanol,decanol, isotridecanol and alcohol mixtures such as those sold by Shellcompanies under the trade mark “LINEVOL”, especially LINEVOL 79 alcoholwhich is a mixture of C₇₋₉ primary alcohols, or a C₁₂₋₁₄ alcohol mixturewhich is commercially available.

The total content of the additives in the diesel fuel composition may besuitably between 0 and 10000 ppmw and preferably below 5000 ppmw.

In the above, amounts (concentrations, % vol, ppmw, % wt) of componentsare of active matter, i.e. exclusive of volatile solvents/diluentmaterials.

Process of Preparing a Liquid Fuel Composition

The liquid fuel composition of the present invention is produced byadmixing:

(a) a component derivable from a water-soluble oxygenated hydrocarbon,with(b) at least one fuel component.

By the term “fuel component” it is meant a component used in thepreparation of a liquid fuel composition, or a liquid fuel compositionper se, which is not a component derived from a water soluble oxygenatedhydrocarbon. Examples of “fuel components” include fuel components thatare currently used in the preparation of gasoline, kerosene and/ordiesel fuel, such as petroleum derived product streams, Fischer-Tropschderived product streams, oxygenates and biofuel components.

Typically, the petroleum derived product streams are product streamsproduced at an oil refinery, also referred to herein as refinerystreams. Non-limiting examples of such refinery streams include:

-   -   “C_(4s)” (light boiling fraction typically comprising greater        than 80% vol paraffinic and olefinic C₄ compounds)    -   Straight Run Tops (SR Tops) or Naphtha (light boiling fraction        of C₄-C₇ hydrocarbons (final boiling point below about 140° C.).        These hydrocarbons are mainly paraffins and have a low octane        rating. The stream is low in aromatics and has some naphthenes.)    -   Isomerate (light boiling fraction (final boiling point below        about 110° C.) obtained by isomerising C₅ and C₆ paraffins in SR        Tops/Naphtha to produce higher octane isomers)    -   Light, full-range (FR) or heavy Platformate (or light,        full-range (FR) or heavy Reformate) (fraction obtained by        catalytic reforming of hydrotreated naphtha to produce a high        octane, high aromatic, low olefin stream)    -   Alkylate (including aviation alkylate) (fraction produced by the        alkylation of isobutane with C₄ and C₃ olefins to produce        high-octane branched chain paraffins)    -   Light or heavy catalytic cracked gasoline (LCCG or HCCG)        (fraction produced by the treatment of heavier streams in a        fluidised catalytic cracker to produce lighter hydrocarbons,        including olefins)    -   Straight run kerosene (fraction containing high levels of        paraffinic hydrocarbons, typically having a distillation        temperature in the range of from about 150° C., +/−10° C., to        about 260° C., +/−about 20° C.)    -   Sweetened kerosene (straight run kerosene that has been treated        to reduce mercaptan levels and also reduce total acid content)    -   Hydrotreated or hydrofined kerosene (mildly hydroprocessed        straight run kerosene that has reduced mercaptan, sulphur,        olefins, acid and metals levels)    -   Severely hydroprocessed kerosene (such as deeply hydrogenated        kerosene, hydrodesulphurised kerosene, hydrocracked kerosene        (straight run kerosene that has been subjected to a more severe        hydroprocessing than hydrotreated kerosene, typically leading to        lower sulphur and nitrogen levels))    -   Straight run distillates boiling in the diesel fuel range    -   Hydrocracked gas oil (AGO)    -   Light cracked and hydrotreated oils from the coker    -   Catalytically cracked gas oil (VGO)    -   Thermally and stream cracked gas oils

The oxygenates and biofuel components are any such component which issuitable for use in a liquid fuel composition, such as those describedhereinbefore.

Process of Preparing a Gasoline Composition

In order to prepare a gasoline composition of the present invention, acomponent derivable from a water-soluble oxygenated hydrocarbon, asdescribed above, in particular the lighter fraction of a componentderived from a water-soluble oxygenated hydrocarbon, is combined with atleast one fuel component.

Typical fuel components which may be admixed with the componentderivable from a water-soluble oxygenated hydrocarbon to prepare agasoline composition according to the present invention include:

-   -   Gasoline compositions per se;    -   Refinery streams, such as C_(4s), SR Tops, Isomerate, Light        Platformate, FR Platformate, Heavy Platformate, Alkylate, LCCG        and HCCG;    -   Oxygenates, such as alcohols and ethers. Preferred oxygenate        components include methanol, ethanol, propanol, butanol, methyl        tertiary-butyl ether (MTBE), and ethyl tertiary-butyl ether        (ETBE); and    -   Biofuel components such as those described hereinbefore.

By the term “gasoline composition” when used in reference to a fuelcomponent, it is meant a composition as defined in the gasolinecomposition section above.

Typically, a gasoline composition of the present invention is preparedby admixing:

-   (a) the lighter fraction of a component derived from a water-soluble    oxygenated hydrocarbon as described above, with-   (b) at least one fuel component selected from a refinery stream.

Preferably, a gasoline composition of the present invention is preparedby admixing:

-   (a) the lighter fraction of a component derived from a water-soluble    oxygenated hydrocarbon as described above, with-   (b) at least one fuel component selected from the refinery streams    C_(4s), SR Tops, Isomerate, Light Platformate, FR Platformate, Heavy    Platformate, Alkylate, LCCG and HCCG; and optionally an oxygenate    selected from ethanol, MTBE and ETBE.

More preferably, a gasoline composition of the present invention isprepared by admixing:

-   (a) the lighter fraction of a component derived from a water-soluble    oxygenated hydrocarbon as described above, with-   (b) at least one fuel component selected from the refinery streams    C_(4s), SR Tops, Heavy Platformate, Alkylate and LCCG; and    optionally ethanol.

Depending upon the amount of the lighter fraction of a component derivedfrom a water-soluble oxygenated hydrocarbon that is used, the amount ofthe fuel components used will be varied to prepare a gasolinecomposition having the desired properties.

For instance, a gasoline composition of the present invention may beprepared by admixing:

-   (a) at least 0.1% vol based on the overall fuel composition of the    lighter fraction of a component derived from a water-soluble    oxygenated hydrocarbon as described above, with-   (b) at least one fuel component selected from the refinery streams    in the following amounts, 1 to 15% vol C_(4s), 3 to 25% vol SR Tops,    0 to 50% vol Heavy Platformate, 5 to 20% vol Alkylate, and 10 to 35%    vol LCCG, based on the overall fuel composition; and optionally up    to 85% ethanol, based on the overall fuel composition.

In the preparation of the gasoline compositions according to the presentinvention, it may be desirable to reduce the relative amount of any SRTops and/or Heavy Platformate in the gasoline composition according tothe present invention with increasing amounts of the lighter fraction ofa component derived from a water-soluble oxygenated hydrocarbon asdescribed above. Therefore, a gasoline composition of the presentinvention may be prepared by substituting at least a portion of any SR

Tops and/or Heavy Platformate used in the preparation of a gasoline withthe lighter fraction of a component derived from a water-solubleoxygenated hydrocarbon as described above.

Alternatively, a gasoline composition of the present invention isprepared by admixing:

-   (a) the lighter fraction of a component derived from a water-soluble    oxygenated hydrocarbon as described above, with-   (b) a gasoline composition.

If the gasoline composition being prepared is an aviation gasoline, thenno oxygenates would be used in the preparation of such an aviationgasoline according to the present invention.

Process of Preparing a Kerosene Composition

In order to prepare a kerosene composition of the present invention, acomponent derivable from a water-soluble oxygenated hydrocarbon, asdescribed above, in particular the moderate fraction of a componentderived from a water-soluble oxygenated hydrocarbon, is combined with atleast one fuel component.

Typical fuel components which may be admixed with the componentderivable from a water-soluble oxygenated hydrocarbon to prepare akerosene composition according to the present invention include refinerystreams, such as straight run kerosene, sweetened kerosene, hydrotreatedor hydrofined kerosene, and severely hydroprocessed kerosene.

Typically, a kerosene composition of the present invention is preparedby admixing:

-   (a) the moderate fraction of a component derived from a    water-soluble oxygenated hydrocarbon as described above, with-   (b) at least one fuel component selected from the refinery streams    straight run kerosene, sweetened kerosene, hydrotreated or    hydrofined kerosene, and severely hydroprocessed kerosene.

Process of Preparing a Diesel Fuel Composition

In order to prepare a diesel fuel composition of the present invention,a component derivable from a water-soluble oxygenated hydrocarbon, asdescribed above, in particular the heavier fraction of a componentderived from a water-soluble oxygenated hydrocarbon, is combined with atleast one fuel component.

Typical fuel components which may be admixed with the componentderivable from a water-soluble oxygenated hydrocarbon to prepare adiesel fuel composition according to the present invention include:

-   -   Diesel fuel compositions per se;    -   Refinery streams, such as straight run distillates boiling in        the diesel fuel range, hydrocracked gas oil (AGO), light cracked        and hydrotreated oils from the coker, catalytically cracked gas        oil (VGO), thermally and stream cracked gas oils;    -   Biofuel components such as those described hereinbefore.

By the term “diesel fuel composition” when used in reference to a fuelcomponent, it is meant a composition as defined in the diesel fuelcomposition section above.

Typically, a diesel fuel composition of the present invention isprepared by admixing:

-   (a) the heavier fraction of a component derived from a water-soluble    oxygenated hydrocarbon as described above, with-   (b) at least one fuel component selected from a refinery stream.

Preferably, a diesel fuel composition of the present invention isprepared by admixing:

-   (a) the heavier fraction of a component derived from a water-soluble    oxygenated hydrocarbon as described above, with-   (b) at least one fuel component selected from the refinery streams    straight run distillates boiling in the diesel fuel range,    hydrocracked gas oil (AGO), light cracked and hydrotreated oils from    the coker, catalytically cracked gas oil (VGO), thermally and stream    cracked gas oils; and optionally a biofuel component.

The present invention further provides a method of operating an internalcombustion engine, jet engine, or a boiler, which method involvesintroducing into a combustion chamber of the engine or boiler, a liquidfuel composition according to the present invention.

The present invention will be further understood from the followingexamples.

EXAMPLES Exemplary Reactor Systems Example 1

FIG. 8 shows a process diagram illustrating one reactor system useful inpracticing the present invention. A feedstock tank 1 acts as a reservoirfor holding the feedstock solutions. The feedstock solution is deliveredfrom the feedstock tank 1 to feed pump 3 through feed line 2, where itis then passed through discharge line 4 to preheater 5. The preheater 5may be a heat exchanger heated by an electrical resistance heater, orany other heat exchanger known in the art. The preheated feed is thenpassed through line 6 and, in some cases, combined with hydrogen 7before entering reactor 9 through line 8. One illustration of apotential reactor 9 is set forth in FIG. 11 and more fully described inExample 4 below.

The temperature of the walls of reactor 9 is maintained by blockheaters, 10 a, 10 b, 10 c, and 10 d, in this case, electrical resistanceheaters. Upon exiting the reactor 9, reaction products enter the reactoroutlet line 11 and are cooled to near ambient temperature in reactorproduct cooler 12, resulting in a potential three phase product stream.From reactor product cooler 12, the reaction products proceed throughline 13 to pressure regulating valve 14, which is used to control thepressure at the reactor outlet if required.

After valve 14, the products enter a phase separator 16 through line 15where it segregates into three separate phases: (1) non-condensable gascomponents 17 containing predominately hydrogen, carbon dioxide,methane, ethane, and propane; (2) an organic liquid fraction 18containing both hydrocarbons and C₃₋₃₀ alcohols, ketones and carboxylicacids; and (3) an aqueous layer 19 containing mostly water and watersoluble oxygenated compounds, such as ethanol, isopropanol, acetone,propanol and acetic acid. The non-condensable gas fraction 17 may berouted through the gas product line 20 to pressure reducing valve 21.The pressure of separator 16 is maintained by pressure reducing valve21. In an alternate mode of operation, the separator 16 may bemaintained at a pressure nearly the same as the reactor outlet byopening or eliminating valve 14. In the alternate mode of operation, thereactor outlet pressure is then controlled by action of pressurereducing valve 21. Gas flow rate and composition are measured uponexiting the system through line 22.

The organic liquid fraction 18 exits the separator through line 23before entering organic draw-off valve 24. The level of organic phasewithin the separator is controlled by adjustment of valve 24. The flowrate and composition of the organic fraction are determined after theorganic fraction exit the system through line 25. The aqueous liquidfraction 19 exits the separator through line 26 before enteringseparator bottoms draw-off valve 27. The level of aqueous phase withinthe separator is controlled by adjustment of valve 27.

The flow rate and composition of the aqueous fraction may be determinedafter the aqueous fraction exits the system through line 28. In analternate mode of operation, both the organic liquid fraction 18 and theaqueous liquid fraction 19 exit the system through the bottom draw-offvalve 27 of the separator and line 28 before being separated in adecanter for measurement of the individual phase compositions and flowrates.

In all cases, the alternate modes of operation do not affect thecatalytic processes being investigated. The alternate modes of operationmay be employed as deemed prudent to achieve optimal control of theprocess, depending on the relative flow rates of the gaseous phase 17,organic liquid phase 18, and aqueous phase 19.

Prior to initiating a flow of feed to the reactors, unless otherwisenoted, catalysts were reduced in a stream of flowing hydrogen at 400°C., regardless of whether a reduction was completed prior to loading thecatalyst into the reactors.

Example 2

FIG. 9 shows a process diagram illustrating another reactor systemuseful for practicing the present invention. This reactor configurationcontains two separate reactors with the capability of operating bothreactors in series or operating only the first reactor. In addition,this configuration allows the catalyst in the second reactor to be takenoff line and regenerated in situ. After regeneration, the second reactormay be returned to service without impacting the first reactoroperation.

The reactor is similar to the reactor of Example 1, except that thereaction products from reactor product cooler 12 could be routed intothe second reactor through line 14 or routed to bypass the secondreactor by passing into line 44. When utilizing the second reactor, flowwould proceed from line 14 to pressure regulating valve 15. Pressureregulating valve 15 may be used to control the pressure at the outlet ofthe first reactor. From pressure regulating valve 15 the flow proceedsto the second reactor inlet isolation valve 17 and into line 18. Fromline 18 the flow continues to line 19 and into the second reactorpreheater 20. In the illustrated embodiment, preheater 20 is a heatexchanger heated by an electrical resistance heater.

The preheated feed is then passed through line 19 into the secondreactor 22, which is more fully described in Example 4. The temperatureof the wall of reactor 22 is maintained by block heaters, 23 a, 23 b, 23c, and 23 d, in this case, electrical resistance heaters. Upon exitingthe reactor, the reaction products enter the second reactor outlet line24 and are then cooled in second reactor product cooler 25. From secondreactor product cooler 26 the process flow may be routed through lines26 and 27 to second reactor outlet isolation valve 28, into lines 29followed by 30 and then into the product separator 31.

When operation of the second reactor is desired, valve 17 and valve 28are open while the second reactor bypass valve 45 is closed to preventthe flow from bypassing the second reactor. When operation of only thefirst reactor is desired, or when the second reactor is beingregenerated, valve 17 and valve 28 are closed while valve 45 is open.When the second reactor is bypassed, the first reactor product flowsdirectly from line 13 into line 44, through bypass valve 45, into line46 and on to line 30. In either case, whether the second reactor is inoperation or bypassed, the flow would proceed from line 30 into theproduct separator.

In phase separator 31, reaction products are separated into a gaseousfraction 32, an organic fraction 33, and an aqueous fraction 34 asdescribed above in Example 1. The gaseous fraction 32 is routed throughthe gas product line 35 to pressure reducing valve 36. The pressure ofseparator 31 is maintained by pressure reducing valve 36. When thesecond reactor 22 is in service, the pressure at the second reactor 22outlet is controlled by action of pressure reducing valve 36. When thesecond reactor 22 is bypassed, the pressure at the outlet of the firstreactor 9 is controlled by action of pressure reducing valve 36.

Gas flow rate and composition are measured upon exiting the systemthrough line 37. The organic liquid fraction 33 exits the separatorthrough line 38 before entering organic draw-off valve 39. The level oforganic phase within the separator is controlled by adjustment of valve39. The flow rate and composition of the organic fraction are determinedafter the organic fraction exits the system through line 40. The aqueousliquid fraction 34 exits the separator through line 41 before enteringseparator bottoms draw-off valve 42. The level of aqueous phase withinthe separator is controlled by adjustment of valve 42. The flow rate andcomposition of the aqueous fraction are determined after the aqueousfraction exits the system through line 43. In an alternate mode ofoperation, both the organic liquid fraction 33 and the aqueous liquidfraction 34 exit the system through the separator bottoms draw-off valve42 and line 43 before being separated in a decanter for measurement ofthe individual phase compositions and flow rates. In all cases, thealternate modes of operation do not affect the catalytic processes beinginvestigated. The alternate modes of operation are employed as deemedprudent to achieve optimal control of the process, depending on therelative flow rates of the gaseous phase 35, organic liquid phase 33,and aqueous phase 34.

Example 3

FIG. 10 shows a process diagram illustrating a dual feed pump reactorsystem useful for practicing the present invention. A dual feed pumpsystem is used when the desired mix of feed components would not existin a single liquid phase. For example, when a mix of 50% by weight2-pentanol and 50% by weight water is the desired feed, two feed pumpsare used, one to deliver 2-pentanol and the other to deliver water. Asimilar system may also be used to mix feedstock derived from twoseparate sources, such as a virgin feedstock and an oxygenatedhydrocarbon feedstock derived from an effluent stream of the reactorsystem itself.

First feedstock tank 1 acts as a reservoir for a first feedstocksolution, while second feedstock tank 40 acts as a reservoir for asecond feedstock solution. A first feed is delivered from firstfeedstock tank 1 to first feed pump 3 through first feed line 2. Thefirst feed is then passed through the first feed pump discharge line 4to combined feed line 44. The second feed is delivered from the secondfeedstock tank 40 to second feed pump 42 through second feed line 41.The second feed is then passed through second feed pump discharge line43 to combined feed line 44. From combined feed line 44 the combinedfeed passes into preheater 5. All other elements are as set forth inExample 1, except that the aqueous phase 19 may be recycled to feedstocktank 40 for further processing or used in other processes.

Example 4

FIG. 11 shows a schematic illustration of one type of reactor which maybe employed in reactor systems as described in Examples 1, 2 and 3.Reactor tube 1 is composed of 316 stainless steel with either an insidediameter of 8.5 mms or an inside diameter of 21.2 mm, depending on theexperiment. Inlet line 2 is provided to allow feedstock or intermediateproduct, such as oxygenates, to enter the reactor. Outlet line 3 isprovided to remove product from the reactor. Inlet frit 4, composed ofstainless steel, acts to secure the beds of preheat media and catalystin place. Preheat media 5, consisting of stainless steel beads, acts asa zone to allow transfer of heat from the reactor walls so that the feedis at the desired temperature upon entering the catalyst 7. A stainlesssteel screen may be placed between preheat media 5 and catalyst 7 toprevent the materials from mixing. Catalyst 7 may be supported inposition by a second stainless steel frit 8.

A thermowell 9 may be installed in some cases to allow measurement ofthe temperatures within catalyst 7 and preheating zone 5. Control oftemperature at the reactor inlet is accomplished by the use of anexternal preheater prior to the feed entering the reactor through line2, and may be further adjusted by control of the heat transfer thatoccurs in the preheat media. In some cases, the preheat media is notrequired to achieve the desired temperature profile. Control of thereactor wall temperature is achieved by the use of external heaters incontact with the outer wall of the reactor. Independently controlledheating zones may be used to control the temperature of the reactor wallas desired.

Example 5 Analysis Techniques

Product streams from the examples described below were analyzed asfollows. The organic liquid phase was collected and analyzed usingeither gas chromatograph with mass spectrometry detection or flameionization detection. Component separation was achieved using a columnwith a bonded 100% dimethyl polysiloxane stationary phase. Relativeconcentrations of individual components were estimated via peakintegration and dividing by the sum of the peak areas for an entirechromatogram. Compounds were identified by comparison to standardretention times and/or comparison of mass spectra to a compiled massspectral database. Gas phase compositions were determined by gaschromatography with a thermal conductivity detector and flame ionizationor mass spectrometry detectors for other gas phase components. Theaqueous fraction was analyzed by gas chromatography with and without aderivatization of the organic components of the fraction using a flameionization detector. Product yields are represented by the feed carbonpresent in each product fraction. The weight hourly space velocity(WHSV) was defined as the weight of feed introduced into the system perweight of catalyst per hour, and based on the weight of the oxygenatedhydrocarbon feed only, excluding water present in the feed.

Production of Oxygenates Example 6 Hydrogenation Catalyst

A hydrogenation catalyst was prepared by adding an aqueous solution ofdissolved ruthenium nitrosyl nitrate to a carbon catalyst support (UUCarbon, Calgon, with particle sizes restricted to those that weremaintained on a 120 mesh screen after passing through an 60 mesh screen)to a target loading of 2.5% ruthenium. Water was added in excess of thepore volume and evaporated off under vacuum until the catalyst was freeflowing. The catalyst was then dried overnight at 100° C. in a vacuumoven.

Example 7 APR/Deoxygenation Catalyst

A combined APR and deoxygenation catalyst was prepared by dissolvinghexachloroplatinic acid and perrhenic acid in water and then adding themixture to a monoclinic zirconia catalyst support (N or ProSaint-Gobain, Product code SZ31164, with particle sizes restricted tothose that were maintained on a 60 mesh screen after passing through an18 mesh screen) using an incipient wetness technique to target aplatinum loading of 1.8% and a rhenium loading of 6.3% on the catalystafter subsequent decomposition of the metal precursors. The preparationwas dried overnight in a vacuum oven and subsequently calcined in astream of flowing air at 400° C.

Example 8 Conversion of Sucrose to Oxygenates

The catalyst systems referenced in Examples 6 and 7 were investigatedfor the conversion of sucrose to an intermediate product containingoxygenates using the reactor system described in Example 1. The studywas conducted using a 21.2 mm internal diameter stainless steel tubereactor shown in Example 4, with an analysis completed as described inExample 5.

31 grams of hydrogenation catalyst from Example 6 and 76 grams of APRcatalyst from Example 7 were loaded into the reactor, with thehydrogenation catalyst on top of the APR catalyst, separated by astainless steel screen. External hydrogen was combined with the feedprior to the feed entering the reactor. Heaters external to the reactor,shown in FIG. 8 as 10 a, 10 b, 10 c, 10 d, were maintained at thefollowing reactor wall temperatures; 10 a—125° C., 10 b—200° C., 10c—265° C., 10 d—265° C., resulting in reactor bed temperatures ofapproximately ˜110-150° C. for hydrogenation, and 150-265° C. for theAPR/Deoxygenation catalyst. The ranges indicate the approximate reactorwall temperatures at the inlet and outlet of each catalyst bed,respectively. Results from the experiment across 39 hours of operationare shown in Table 1. The WHSV is based on the weight of theAPR/Deoxygenation catalyst. Total mono-oxygenates includes alcohols,ketones, tetrahydrofurans and cyclic mono-oxygenates. Cyclicmono-oxygenates includes compounds in which the ring does not includeoxygen, such as cyclopentanone and cyclohexanone. The fraction of feedcarbon contained within unknown components in the aqueous phase wasdetermined as the difference of carbon accounted for by known, measuredcomponents and the total organic carbon.

TABLE 1 Conversion of Sucrose to Oxygenates Across a Hydrogenation andAPR Catalyst Hours on Stream 5 16 27 39 WHSV wt_(feed)/(wt_(catalyst)hr) 1.8 1.8 1.7 1.5 Added Hydrogen mol_(H2)/mol_(feed) 3.4 3.4 3.6 4.0Organic Phase Yield % of feed carbon 27 25 20 22 Breakdown of ReactorOutlet Composition Carbon Dioxide % of feed carbon 19.4 21.2 18.1 17.7Paraffins % of feed carbon 14.1 13.5 9.2 10.8 Mono-oxygenates % of feedcarbon 31.5 30.6 27.5 30.8 Alcohols % of feed carbon 11.1 11.8 11.2 11.6Ketones % of feed carbon 8.2 7.0 7.1 9.0 Tetrahydrofurans % of feedcarbon 10.6 10.7 8.1 8.6 Cyclic % of feed carbon 1.6 1.1 1.1 1.5Mono-oxygenates Unknown Aqueous % of feed carbon 21.2 27.8 28.3 32.0Species

Example 9 APR/Deoxygenation Catalyst

A catalyst was prepared as described in Example 7, except that thecatalyst support was a tetragonal zirconia (N or Pro Saint-Gobain,Product code SZ61152) with particle sizes restricted to those that weremaintained on a 60 mesh screen after passing through an 18 mesh screen.

Example 10 APR/Deoxygenation Catalyst

Hexachloroplatinic acid and perrhenic acid dissolved in water were addedto a monoclinic zirconia catalyst support (N or Pro Saint-Gobain,Product code SZ61164, with particle sizes restricted to those that weremaintained on a 60 mesh screen after passing through an 18 mesh screen)using an incipient wetness technique to target a platinum loading of1.9% and a rhenium loading of 1.8% on the catalyst after subsequentdecomposition of the metal precursors. The preparation was driedovernight in a vacuum oven and subsequently calcined in a stream offlowing air at 400° C.

Example 11 APR/Deoxygenation Catalyst

A catalyst was prepared as described in Example 7 except that thesupport was a hydrogen peroxide functionalized activated carbon. Thesupport was first prepared by adding activated carbon (Calgon UU 60×120mesh carbon) slowly to a 30% hydrogen peroxide solution, with themixture then left overnight. The aqueous phase was decanted and thecarbon was washed three times with deionized water, and then dried undervacuum at 100° C. A solution of hexachloroplatinic acid and perrhenicacid in water was then added to the support using an incipient wetnesstechnique to target a platinum loading of 1.8% and a rhenium loading of6.3% after subsequent decomposition of the metal precursors. Thepreparation was dried overnight in a vacuum oven at 100° C.

Example 12 Conversion of Sorbitol and Glycerol

The catalyst systems referenced in Example 9, Example 10, and Example11, were investigated for the conversion of sorbitol or glycerol to anintermediate product containing oxygenates using the reactorconfiguration described in Example 1, with an analysis completed asdescribed in Example 5. The study was conducted using the 8.5 mminternal diameter stainless steel tube reactor shown in Example 4. Inall cases, the reactor pressure was maintained at 625 psig. Reactorinlet and outlet temperatures, shown in Table 2 were controlled usingheaters external to the reactor as shown in FIG. 8 as 10 a, 10 b, 10 c,10 d. Results of these experiments are shown in Table 2.

Table 2 shows the impact of catalyst composition, feedstock composition,and operating conditions on the conversion performance. FIG. 12 showsthe carbon number distribution of the mono-oxygenates produced inExperiment D and Experiment E. The primary difference between these twoexperiments was the reaction temperature. For Experiment D,mono-oxygenates containing three or fewer carbon atoms predominatedwhile for Experiment E, a significant fraction of the mono-oxygenatescontained four or more carbon atoms, indicating that condensationreactions were occurring within the same reaction zone as the hydrogengeneration and deoxygenation reactions. The WHSV is based on the weightof the APR/Deoxygenation catalyst. The net hydrogen produced is thehydrogen present at the reactor outlet as H₂, which does not includehydrogen produced and consumed in situ. Total mono-oxygenates includealcohols, ketones, tetrahydrofurans and cyclic mono-oxygenates. Cyclicmono-oxygenates include compounds in which the ring does not includeoxygen, such as cyclopentanone and cyclohexanone. The fraction of feedcarbon contained within unknown components in the aqueous phase wasdetermined as the difference of carbon accounted for by known, measuredcomponents and the total organic carbon.

TABLE 2 Conversion of Polyols to Oxygenates Across a APR/DeoxygenationCatalyst Experiment A B C D E Feed 50% 50% 65% 50% 50% Sorbitol SorbitolSorbitol Glycerol Glycerol Catalyst Composition Example No. 11 9 10 1010 WHSV wt_(feed)/(wt_(catalyst) 2.1 1.8 1.7 1.5 1.5 hr) Catalyst InletTemp. ° C. 241 240 240 260 310 Catalyst Outlet ° C. 240 241 321 260 350Temperature Net Hydrogen Produced mol_(H2)/mol_(feed) 0.6 0.9 0.7 1.20.7 Organic Phase Yield % of feed carbon 17 24 38 0 38 Breakdown ofReactor Outlet Composition Carbon Dioxide % of feed carbon 32.4 34.023.5 31.3 16.0 Paraffins % of feed carbon 37.4 25.3 7.8 6.6 7.4 TotalMono-oxygenates % of feed carbon 33.9 32.9 40.0 45.9 41.0 Alcohols % offeed carbon 6.3 8.5 2.6 40.6 4.6 Ketones % of feed carbon 23.5 16.9 15.25.2 24.1 Tetrahydrofurans % of feed carbon 4.1 7.2 10.7 0.1 2.7 CyclicMono-oxygenates % of feed carbon 0.0 0.4 11.6 0.0 9.7 Unknown AqueousSpecies % of feed carbon 1.2 7.8 15.8 30.4 10.7

Condensation of Oxygenates Using Basic Catalysts Example 13

A zinc aluminate catalyst support was prepared by mixing zinc oxidepowder and alumina powder (Dispal 18N4-80, Sasol North America, Houston,Tex.) to a target ratio of 1.0 moles of ZnO to 1 mole of Al₂O₃. Dilutenitric acid was then added at a level of 1 wt % HNO₃ to alumina. Thedough consistency of the mixture was adjusted with water addition toform a workable dough, which was then extruded using a laboratory scaleextruder. The extrudates were dried overnight under vacuum at 100° C.,then further dried at 200° C. for one hour under flowing air, and thensubsequently calcined at 750° C. for 4 hours under flowing air. Theresulting material was then ground and sieved. Material that wasmaintained on a 60 mesh screen after passing through an 18 mesh screenwas recovered.

Example 14

Hexachloroplatinic acid was added to the calcined material of Example 13using an incipient wetness impregnation technique to achieve a targetplatinum loading of 1.0 wt %. The catalyst was dried overnight undervacuum at 100° C. and calcined at 400° C. under flowing air.

Example 15

Palladium nitrate was added to the calcined material of Example 13 usingan incipient wetness impregnation technique to achieve a targetpalladium loading of 0.5 wt %. The catalyst was dried overnight undervacuum at 100° C. and calcined at 400° C. under flowing air.

Example 16

A copper zinc aluminate catalyst was prepared by mixing zinc oxide,copper (I) oxide, and alumina powder (Dispal 18N4-80) at a target ratioof 0.11 moles of CuO and 0.9 moles of ZnO to one mole of Al₂O₃. Dilutenitric acid was then added at a level of 1 wt % HNO₃ to alumina. Thedough consistency of the mixture was adjusted with water addition toform a workable dough, which was then extruded using a laboratory scaleextruder. The extrudates were dried overnight under vacuum at 100° C.,then further dried at 200° C. for one hour under flowing air, and thensubsequently calcined at 750° C. for 4 hours under flowing air. Theresulting material was then ground and sieved. Material that wasmaintained on a 60 mesh screen after passing through an 18 mesh screenwas recovered.

Example 17

A cesium modified silica-alumina catalyst was prepared by adding cesiumcarbonate dissolved in water to Siralox silica-alumina catalyst support(Sasol North America, Houston, Tex.). The target loading of cesium was25 wt % based on final catalyst weight. This material was dried for 24hours under vacuum at 100° C. and calcined at 500° C. for 6 hours underflowing air. After calcining, platinum was added using an incipientwetness impregnation technique to achieve a final platinum loading of 1wt %. After impregnation, the catalyst was dried and then calcined at500° C. for 6 hours under flowing air.

Example 18

A cerium modified silica was prepared by adding cerium nitrate solutionto a silica gel (Davisil grade 636, WR Grace Company) to a final loadingof 25 wt % CeO₂. The resulting material was then dried at 120° C. forsix hours and further calcined at 550° C. for six hours under flowingair. Palladium nitrate was added to the calcined material using anincipient wetness impregnation technique to achieve a target palladiumloading of 0.5 wt %. This material was then dried at 120° C. for sixhours and further calcined at 550° C. for six hours under flowing air.

Example 19

The catalyst systems referenced in Examples 14-18 were investigated forthe vapor-phase condensation of various oxygenates. The studies wereconducted using 8.5 mm and 21.2 mm internal diameter size stainlesssteel tube reactors as described in Example 4 and in the reactor systemsillustrated by FIGS. 8 and 10. Between 15 and 18 milliliters of catalystwas loaded into the smaller reactor, with between 50 and 70 millilitersof catalyst loaded into the larger reactor. In all cases the catalystwas reduced at 400° C. under flowing hydrogen prior to use.

The organic liquid phase was collected and analyzed as described inExample 5. Table 3 shows organic product yields and composition as afunction of operating conditions, feedstock composition, and the addedmetal component for the catalysts described in Examples 14-18 above.Greater than 100% reported organic phase yields stem from experimentaluncertainty in the measurement of process stream flow rates orcomposition. Non-condensed components are those components that do notrequire the formation of new carbon-carbon bonds to be produced from thegiven feed. For simplicity, all compounds containing five or fewercarbon atoms are considered to be non-condensed components. Totalcondensation products are those compounds containing six or more carbonatoms, which require the formation of new carbon-carbon bonds to beformed from the given feedstocks.

Experiments F and G demonstrate that product selectivity can be affectedby the choice of hydrogenation function, e.g. Pt or Pd. Paraffins wereproduced to a larger extent over the catalyst containing 1% platinumcompared to the catalyst containing 0.5% palladium. The later favoredthe production of mono-oxygenates, primarily ketones. Experiments H andI further reinforce this concept. Experiment H shows that condensedmono-oxygenate components can be obtained at high yield with isopropylalcohol as a feed, accounting for >97% of the organic product andcontaining >90% of the overall carbon at the reactor outlet. Byincreasing the reaction temperature and using copper to drive thehydrogenation reactions, the selectivity can be shifted to obtain asignificant yield of olefins (Experiment I). Experiments J, K and L showthat a number of other heterogeneous catalysts can be used to promotethe condensation of oxygenates followed by hydrogenation of the initialcondensation products. Experiments K and L show that as the temperatureis decreased from 300° C. to 250° C., the rate of condensation drops sothat the conversion to condensed products drops from 81 wt % to 18 wt %in the resulting organic phase.

TABLE 3 Vapor Phase Condensation of Oxygenates Over Basic Catalysts 1%Pt/Cs Impregnated 0.5% Pd/ 0.5% Pd/ Siralox Ce Ce 1% Pt/ 0.5% Pd/ 0.5%Pd/ CuO/ZnO/ Silica- Modified Modified Catalyst ZnO/Al2O3 ZnO/Al2O3ZnO/Al2O3 Al2O3 Alumina Silica Silica Experiment F G H I J K L Feed FeedA Feed A Feed B Feed B Feed A Feed B Feed B WHSV wt_(feed)/ 1 1.5 1.5 21.1 1.9 1.9 (wt_(cat) hr) Added Hydrogen mol_(H2)/ 1 1 0 0 1 0 0mol_(feed) Temperature ° C. 375 375 300 375 325 300 250 Pressure Psig600 600 600 625 600 600 600 Organic Phase % of feed 75 99 95 55 107 7498 Yield carbon Organic Phase Composition Breakdown C5− wt % 9.6 7.3 0.02.4 1.6 0.0 0.0 Hydrocarbons C5− Oxygenates wt % 6.2 20.9 1.9 14.6 75.818.5 81.8 Total Non- wt % 15.8 28.2 1.9 16.9 77.4 18.5 81.8 CondensedComponents C6+ Paraffins wt % 49.5 18.9 0.3 1.0 0.0 20.1 0.2 C6+ Olefinswt % 4.6 0.0 0.0 15.9 0.0 0.0 0.0 Other C6+ wt % 0.0 0.0 0.0 1.1 0.0 0.00.0 Hydrocarbons C6+ Mono- wt % 30.2 51.8 97.3 64.5 22.6 61.0 18.0oxygenates Total Cond. wt % 84.2 70.7 97.6 82.5 22.6 81.1 18.2 ProductsFeed A - 49.5% 2-Pentanone, 50.5% 2-Pentanol Feed B - 100% IsopropylAlcohol

Condensation of Oxygenates Using Acid-Base Catalysts Example 20

A hydrotalcite catalyst was prepared from a commercially availablehydrotalcite support (ESM-350, ASM Catalysts, Baton Rouge, LA) bygrinding the material and passing through graduated screens to achieveparticles sizes larger than 60 mesh and less than 18 mesh. The materialwas then calcined in a quartz tube reactor at 450° C. for 6 hours underflowing nitrogen.

Example 21

Platinum was added to the hydrotalcite catalyst of Example 20 using anincipient wetness impregnation technique to achieve a final targetplatinum loading of 1 wt %. The platinum containing precursor washexachloroplatinic acid, H₂PtCl₆. The impregnated material was driedovernight under vacuum at 100° C. and subsequently calcined at 400° C.for 2 hours under flowing air.

Example 22

Platinum and tin were added to the hydrotalcite catalyst of Example 20using an incipient wetness impregnation technique to achieve a finaltarget loading of 1 wt % Pt and 0.2 wt % Sn. The platinum containingprecursor was hexachloroplatinic acid, H₂PtCl₆ while tin was derivedfrom tin chloride, SnCl₂*2H₂O. The impregnated material was driedovernight under vacuum at 100° C. and subsequently calcined at 450° C.for 8 hours under flowing nitrogen.

Example 23

A 5% magnesium oxide catalyst supported on granular zirconia wasprepared using an incipient wetness impregnation technique to achieve afinal target loading of 5 wt % Mg. Magnesium was added as magnesiumnitrate and dried overnight under vacuum at 100° C. and subsequentlycalcined at 450° C. for 8 hours under flowing air. An aqueous palladiumnitrate solution was added to the calcined material to achieve a targetpalladium loading of 0.5 wt % using an incipient wetness impregnationtechnique. The catalyst was dried a second time and calcined at 400° C.for six hours under flowing air.

Example 24

A zinc aluminate catalyst support was prepared by mixing zinc oxidepowder and alumina powder (Dispal 18N4-80, Sasol North America, Houston,Tex.) to a target ratio of 0.85 moles of ZnO to 1 mole of Al₂O₃. Dilutenitric acid was added at a level of 1 wt % HNO₃ to total solids. Thedough consistency was adjusted with water addition to form a workabledough suitable for extrusion and the mixture was extruded using alaboratory scale extruder. The extrudates were dried overnight undervacuum at 100° C. and subsequently calcined at 750° C. for 8 hours underflowing air. The material was then sized to 18 by 60 mesh. An aqueouspalladium nitrate solution was added to the calcined material to achievea target palladium loading of 0.5 wt % using an incipient wetnessimpregnation technique. This catalyst was then dried a second time andcalcined at 400° C. for six hours under flowing air.

Example 25

The catalyst systems referenced in Examples 21-24 were used to conductvapor-phase condensation reactions with various oxygenates. The studieswere conducted using 8.5 mm and 21.2 mm internal diameter size stainlesssteel tube reactors as described in Example 4 and reactor systems asillustrated in Examples 1 and 3. Between 15 and 18 milliliters ofcatalyst was loaded into the smaller reactor, with between 50 and 70milliliters of catalyst loaded into the larger reactor. In all cases thecatalyst was reduced at 400° C. under flowing hydrogen prior to use.

The organic liquid phase was collected and analyzed as described inExample 5. Table 4 shows the organic product yields and composition as afunction of operating conditions, feedstock composition, and the addedmetal component for the hydrotalcite catalysts described in Examples 21and 22 above. The data from the experiments show that a primarilyhydrocarbon product can be formed from acetone and isopropyl alcohol inthe absence of an added metal hydrogenation component. In Experiment M,the organic phase product contained primarily nine carbon methylsubstituted cyclohexenes, categorized as other C₆+ hydrocarbons in Table4. The addition of platinum (Experiment N) to this catalyst favored theformation of condensed mono-oxygenate products, mainly ketones andalcohols, and the formation of some paraffins as a result ofdeoxygenation of the ketones and alcohols. The selectivity was furthershifted in favor of condensed mono-oxygenates by attenuating theplatinum with tin and operating at a higher pressure (Experiment O).Experiments P, Q, R and S illustrate the impact of reaction temperaturefor the condensation of a mixed feed containing pentanol and pentanone.As the reaction temperature was raised from 300° C. to 375° C., agradual change in product composition became apparent, with theselectivity to condensed mono-oxygenates decreasing and the selectivityto condensed paraffins increasing as the temperature was raised.

Table 5 shows the impact of feedstock components and reactiontemperature on organic product yields and composition for the catalystsof Examples 23 and 24. Experiments T and U compare the condensation of2-pentanone and 2-methyltetrahydrofuran. Overall, the condensation of2-pentanone is faster than 2-methyltetrahydrofuran. Nonetheless, around30% of the tetrahydrofuran was converted to condensation products underthese conditions. Experiments 10 and 11 show the impact of reactiontemperature when using a pure isopropyl alcohol feed. At 300° C.(Experiment V), mono-oxygenated condensation products predominate, whileat 400° C. (Experiment W) a significant portion of the productsconsisted of hydrocarbons. Compared to other experiments listed inTables 4 and 5, Experiment W is notable in that the organic productcontained a higher level of olefins. The addition of valeric acid to thefeed (Experiment X) suppressed overall condensation rates and shiftedthe selectivity away from paraffins and towards other hydrocarbons,primarily substituted aryl compounds.

Greater than 100% reported organic phase yields stem from experimentaluncertainty in the measurement of process stream flow rates orcomposition. Non-condensed components are those components that do notrequire the formation of new carbon-carbon bonds to be produced from thegiven feed. For simplicity, all compounds containing five or fewercarbon atoms are considered to be non-condensed components. Totalcondensation products are those compounds containing six or more carbonatoms, which require the formation of new carbon-carbon bonds to beformed from the given feedstocks.

TABLE 4 Vapor Phase Condensation of Oxygenates Over HydrotalciteCatalysts 1% Pt, 1% Pt, 1% Pt, 1% Pt, 1% Pt, Metal Function None 1% Pt0.2% Sn 0.2% Sn 0.2% Sn 0.2% Sn 0.2% Sn Experiment M N O P Q R S FeedFeed C Feed C Feed C Feed A Feed A Feed A Feed A WHSV wt_(feed)/ 1.0 0.90.7 0.7 0.7 0.7 0.7 wt_(cat) hr Added Hydrogen mol_(H2)/ 0.5 0 0 1 1 1 1mol_(feed) Temperature ° C. 350 350 350 300 325 350 375 Pressure Psig100 100 600 600 600 600 600 Organic Phase Yield % of 61 95 91 108 104108 85 feed carbon Organic Phase Composition Breakdown C5− Hydrocarbonswt % 2.8 3.6 1.0 4.6 7.1 9.4 20.0 C5− Oxygenates wt % 11.9 16.0 5.8 41.921.4 13.7 8.8 Total Non-Condensed wt % 14.7 19.6 6.8 46.5 28.5 23.1 28.8Components C6+ Paraffins wt % 0.0 13.1 7.6 2.2 11.3 28.6 53.0 C6+Olefins wt % 5.1 1.2 1.0 0.0 0.2 0.0 0.0 Other C6+ wt % 72.8 0.0 0.0 0.00.0 0.0 0.0 Hydrocarbons C6+ Mono-oxygenates wt % 5.7 54.3 80.4 51.460.1 47.8 18.2 Total Condensation wt % 83.5 68.6 89.0 53.6 71.6 76.571.2 Products Feed A - 49.5% 2-Pentanone, 50.5% 2-Pentanol Feed C - 50%Isopropyl Alcohol, 50% Acetone

TABLE 5 Vapor Phase Condensation of Oxygenates Over MagnesiumImpregnated Zirconia and Zinc Aluminate Catalysts 0.5% Pd/Zinc 0.5%Pd/Zinc 0.5% Pd/Zinc 0.5% Pd/ 0.5% Pd/ Aluminate Aluminate Aluminate 5%Mg 5% Mg (0.85:1 (0.85:1 (0.85:1 Catalyst Zirconia Zirconia ZnO:Al₂O₃)ZnO:Al₂O₃) ZnO:Al₂O₃) Experiment T U V W X Feed Feed D Feed E Feed BFeed B Feed F WHSV wt_(feed)/ 2 2 1 1 1 (wt_(cat) hr) Added Hydrogenmol_(H2)/ 1 1 0 0 0 mol_(feed) Temperature ° C. 400 400 300 400 400Pressure psig 600 625 600 600 600 Organic Phase % of feed 85 76 104 5853 Yield carbon Organic Phase Composition Breakdown C5− Hydrocarbons wt% 7.4 4.0 0.4 2.8 2.0 C5− Oxygenates wt % 21.4 66.5 5.2 6.9 17.3 TotalNon- wt % 28.8 70.6 5.6 9.7 19.3 Condensed Components C6+ Paraffins wt %22.1 10.9 3.4 17.1 5.6 C6+ Olefins wt % 0.0 2.8 0.0 23.8 13.6 Other C6+wt % 1.3 0.3 0.0 8.1 19.8 Hydrocarbons C6+ Mono- wt % 46.5 14.7 90.841.2 38.6 oxygenates Total Cond. wt % 69.9 28.8 94.2 90.1 77.7 ProductsFeed B - 100% Isopropyl alcohol Feed D - 100% 2-pentanone Feed E - 100%2-methyltetrahydrofuran Feed F - 90% Isopropyl alcohol, 10% Valeric Acid

Base Condensation of Oxygenates Followed by Deoxygenation Example 26

A zinc aluminate catalyst support was prepared similar to that inExample 13 except that the amount of zinc oxide was reduced to target aratio of 0.85 moles of ZnO to 1 mole of Al₂O₃.

Example 27

Hexachloroplatinic acid was added to the calcined material of Example 26using an incipient wetness impregnation technique to achieve a targetplatinum loading of 1.0 wt %. The catalyst was dried overnight undervacuum at 100° C. and calcined at 400° C. under flowing air.

Example 28

The catalyst systems referenced in Examples 27 and 15 were investigatedfor the vapor-phase condensation of various oxygenates and subsequentconversion to hydrocarbons. The studies were conducted using 21.2 mminternal diameter size stainless steel tube reactors as described inExample 4, and reactor systems as illustrated by Examples 2 and 3.Approximately 100 milliliters of each catalyst was loaded into twoseparate reactors. The two reactors were arranged so that the effluentof the first reactor flowed into the second reactor. The first reactorcontained the catalyst of Example 15 and the second reactor containedthe catalyst of Example 27. The catalyst was reduced at 400° C. underflowing hydrogen prior to use. In all cases, hydrogen was combined withthe feed prior to entering the reactor.

Products were separated and analyzed as described in Example 5. Table 6shows organic product yields and composition as a function of operatingconditions and feedstock composition obtained from the consecutivereactions. Non-condensed components are those components that do notrequire the formation of new carbon-carbon bonds to be produced from thegiven feed. For simplicity, all compounds containing five or fewercarbon atoms are considered to be non-condensed components. Totalcondensation products are those compounds containing six or more carbonatoms, which require the formation of new carbon-carbon bonds to beformed from the given feedstocks.

Experiments AA, BB, CC, and DD demonstrate that various oxygenates canbe employed in the consecutive condensation and deoxygenation reactionsto yield a product containing primarily C₆₊ alkanes. The productscontain a larger fraction of alkanes and low levels of oxygenatedcompounds compared to the results shown in Table 3. This demonstratesthat the use of catalysts with different functionalities (i.e. abasic+hydrogenation catalyst in a first reactor followed byacid+basic+hydrogenation catalyst in the second reactor) can be moreeffective for the production of hydrocarbons from oxygenated compoundsthan the use of a catalyst that contains only basic and hydrogenationfunctionality. In Experiment EE, the organic product produced inExperiments AA through DD was recycled through the reaction system.After this treatment, the final product contained primarily alkanes withonly traces of oxygen containing components. The hydrocarbons thusproduced would be valuable for use as liquid fuels such as gasoline,diesel, and jet fuel.

TABLE 6 Vapor Phase Condensation and Deoxygenation of OxygenatesExperiment AA BB CC DD EE Feed Feed B Feed G Feed D Feed H Feed I WHSVwt_(feed)/(wt_(cat) hr) 1.9 2.2 2.1 2.0 2.0 Added Hydrogenmol_(H2)/mol_(feed) 1.5 1.7 2 2 >2 Reactor 1 Temperature ° C. 300 300300 300 325 Reactor 2 Temperature ° C. 350 375 375 375 375 Pressure psig625 625 625 625 625 Organic Phase Yield % of feed carbon 81 76 80 93 87Product Composition Breakdown C5− Hydrocarbons % of feed carbon 8 11 1533 15 C5− Oxygenates % of feed carbon 3 2 2 4 0 Total Non-CondensedComponents % of feed carbon 11 13 18 37 15 C6+ Alkanes % of feed carbon71 71 65 56 74 C6+ Alkenes % of feed carbon 0 0 0 0 0 Other C₆₊Hydrocarbons % of feed carbon 0 0 0 0 0 C₆₊ Mono-oxygenates % of feedcarbon 6 5 3 2 0 Total Products (Condensation) % of feed carbon 77 76 6858 74 Feed B - 100% Isopropyl Alcohol Feed D - 100% 2-pentanone Feed G -50% Isopropyl Alcohol, 50% 2-Pentanone Feed H - 50% Acetone, 50%2-Pentanone Feed I - Organic Phase From AA-DD

Product Fractionation Example 29

The material of Experiment EE of Example 28 was collected and subjectedto a distillation step. The distillation was conducted at atmosphericpressure using a simple, single stage laboratory batch distillationapparatus. 2.950 liters of liquid product was added to a heated roundbottomed flask which acted at the reboiler at the beginning of theexperiment. The overhead product was condensed and segregated intoseparate samples based on the temperature of the vapor phase inequilibrium with the boiling liquid, with an analysis of the fractionscompleted as described in Example 5. The carbon number distribution ofthe product fractions is shown in Table 7. All fractions containedprimarily alkanes.

The fractions recovered with a boiling point less than 150° C. containalkanes mainly in the C₅₋₁₀ range and would be suitable as a gasolineblending component. The higher boiling point range materials could bepotentially useful for incorporation into distillate fuels, kerosene anddiesel.

Example 30

The distilled product boiling in the range of 150° C. to 250° C. wasanalyzed for suitability as a Jet Fuel by a commercial testing service(Intertek Testing Services, Ill.) according to ASTM testing methodD1655. The sample passed all required specifications with the exceptionof the flash point and density specifications. It is probable that theflash point specification could be met through adoption of improvedproduct distillation, while the low density may be attributed to thehigh levels of alkanes in the sample.

TABLE 7 Results from Distillation of the Product of Example 30 Boiling °C. Starting Less 100 to 150 to Greater Range Material than 100 150 250than 250 Volume ml 2950 750 750 1300 180 Recovered Total wt % 99.8 100.0100.0 99.4 91.4 Alkanes Carbon Breakdown by Species Carbon Number NumberC⁴⁻ wt % 0.2 0.4 C₅₋₉ wt % 52.6 96.0 78.1 13.7 C₁₀₋₁₄ wt % 41.3 3.6 21.978.3 29.9 C₁₅₊ wt % 5.7 7.4 61.5

Production of C5+ Compounds from Glycerol Using a Single CatalyticSystem Example 31

A bimetallic catalyst system containing platinum and rhenium (5 wt %platinum with a molar ratio of Pt:Re of 1:2.5) supported on activatedcarbon (Calgon UU 60×120 mesh carbon) was prepared using incipientwetness techniques. Activated carbon was added slowly to a 30% hydrogenperoxide solution. After addition of the carbon was completed, themixture was left overnight. The aqueous phase was decanted and thecarbon was washed three times with of deionized water, and then driedunder vacuum at 100° C. An aqueous solution, with a volume equal toincipient wetness volume for the carbon to be impregnated, 10.4 mL, andcontaining dihydrogen hexachloroplatinate (IV) hexahydrate (Alfa Aesar,39.85% Pt) and perrhemic acid solution (Alfa Aesar, 76.41% HReO₄) wasapplied drop wise, while stirring, to hydrogen peroxide functionalizedcarbon. The wetted carbon was dried at 100° C. under vacuum.

Example 32

104.4 grams of the 1:2.5 Pt/Re catalyst were loaded into a 63.5 cm longreactor tube as described in Example 4 and Example 1, except that thetemperature profile was controlled by heat exchange with a hot airstream provided by a blower and heater as illustrated in FIG. 7. Thecatalyst was reduced with flowing hydrogen at 350° C. for two hoursbefore liquid feed was introduced to the catalyst bed. A 50 wt %glycerol (Colgate Palmolive USP Grade) containing about 20 ppm sulfatein water solution was fed downflow across the reactor after beingpreheated to 182° C. at a weight hourly space velocity of 0.97 grams ofglycerol per gram of catalyst per hour. Hot air was fed upflow throughthe annular space at 409° C. The axial temperature profile within thecenter of the catalyst bed was measured using a sliding thermocouple asshown in Example 4, and is illustrated in FIG. 13. The separatorpressure was maintained at 600 psig. The effluent from the reactor wascooled down with a water cooled condenser and separated in a three-phaseseparator. The gas-phase products were analyzed with a gas chromatographthat allowed the analysis of hydrogen, carbon dioxide, methane, ethane,propane, butane, pentane, and hexane. An organic phase was collected,weighed, and sent to Southwest Research Institute (San Antonio, Tex.)for gasoline analysis. The aqueous-phase was collected and weighed, andthen analyzed using both a GCMS as well as GC-FID. In this system, therewas complete conversion of the glycerol. Table 8 below shows the yieldsof hydrogen as well as the yields of carbon containing productcompounds.

TABLE 8 Yields for the Conversion of Glycerol from Example 32 Productsmoles of H2/mole of glycerol feed 1.03 % Carbon/Carbon in Feed CO2 31.79Methane 7.35 Ethane 7.28 Propane 5.25 Butane 0.56 Pentane 1.40 Hexane2.05 C7-C13 Normal 0.87 C4-C13 Iso 2.87 C6-C12 Aromatic 3.87 C8-C11Naphthalene/Napthenes 1.89 C5-C10 Olefins 5.67 C4-C6 OxygenatedCompounds in 1.86 Organic Phase Ethanol in Aqueous Phase 0.39 AceticAcid in Aqueous Phase 1.33 Acetone in Aqueous Phase 13.19 Propionic Acidin Aqueous Phase 4.69 Propylene Glycol in Aqueous Phase 2.79 1-Propanolin Aqueous Phase 1.71 Isopropyl Alcohol in Aqueous Phase 1.28 C4/C5/C6in Aqueous Phase 2.20

Production of C5+ Compounds from Sugar Alcohols Example 33

Experiments were conducted with aqueous solutions of oxygenatedhydrocarbons (e.g., 50 wt. % glycerol/water mixture or 50 wt %sorbitol/water mixture) introduced in to the reactor system ofExample 1. The feedstock was further modified by the addition of K₂SO₄at various concentrations (1, 20, or 50 ppm).

Example 34

A total of 10.61 grams of the 1:2.5 Pt/Re catalyst were loaded into the8.5 mm stainless steel reactor tube described in Example 4. The catalystwas reduced with flowing hydrogen at 350° C. for two hours before liquidfeed was introduced to the catalyst bed. A 50 wt % glycerol solutioncontaining about 1 ppm sulfate in water solution was fed downflow acrossthe reactor at a WHSV of 1.24 grams of glycerol per gram of catalyst perhour. Subsequent tests were performed with 20 ppm and 50 ppm sulfateadded as K₂SO₄. The block heaters were controlled at 260° C. and theseparator pressure was maintained at 600 psig.

An organic phase was collected from the separated, weighed, and analyzedwith a GC-MS as described in Example 5. Table 9 below shows the yieldsof hydrogen as well as the yields of carbon containing product compoundswith the different amounts of sulfate added to the system. In thissystem, there was complete conversion of the glycerol. The table showsthat a liquid organic phase was generated with the addition of sulfategreater than 20 ppm.

TABLE 9 Yields of Hydrogen and Carbon Containing Products from Example34 K₂SO₄ loading Sulfate 1 20 50 Block 1 Temperature (° C.) (FIG. 8,10a) 260 260 260 Block 2 Temperature (° C.) (FIG. 8, 10b) 260 260 260Block 3 Temperature (° C.) (FIG. 8, 10c) 260 260 260 Block 4 Temperature(° C.) (FIG. 8, 10d) 260 260 260 H₂ produced/mole of glycerol feed 1.671.26 0.72 % Carbon/Carbon in Feed CO₂ 48.9% 44.4% 27.4% CH₄ 14.5% 12.7%6.1% C₂H₆ 18.9% 16.0% 6.0% C₃H₈ 9.4% 7.4% 4.8% C₄H₁₀ 0.6% 0.7% 0.2%C₅H₁₂ 1.0% 1.0% 0.3% C₆H₁₄ 1.1% 0.7% 0.1% C₆ ⁺ Hydrocarbons in OrganicPhase 0.0% 0.4% 5.4% C₂-C₆ Oxygenates in Organic Phase 0.0% 1.7% 7.9%C₂-C₆ Oxygenates in Aqueous Phase 6.9% 13.3% 42.6%

Example 35

A total of 10.61 grams of the 1:2.5 Pt/Re catalyst were loaded into the8.5 mm stainless steel reactor tube described in Example 4 and thereactor system illustrated in Example 1. The catalyst was reduced withflowing hydrogen at 350° C. for two hours before liquid feed wasintroduced to the catalyst bed. A 50 wt % glycerol solution containingeither 1 ppm or 20 ppm sulfate in water was fed downflow across thereactor at a WHSV of 1.24 grams of glycerol per gram of catalyst perhour. The block heaters were controlled such that the first 10.1 cm ofthe reactor was held at 260° C., the second 10.1 cm of the reactor wasat approximate 306° C., the next 10.1 cm of the reactor was atapproximately 355° C., and the last 10.1 cm of the reactor at 400° C.The separator pressure was maintained at 600 psig.

The effluent from the reactor was cooled down with a water cooledcondenser, separated in a three-phase separator, and then analyzed asdescribed in Example 5. In this system, there was complete conversion ofthe glycerol. Table 10 below shows the yields of hydrogen as well as theyields of carbon containing product compounds.

TABLE 10 Yields of Hydrogen and Carbon Containing Products from Example35 K₂SO₄ loading Sulfate 1 20 Block 1 Temperature (° C.) 260 260 Block 2Temperature (° C.) 307 305 Block 3 Temperature (° C.) 354 356 Block 4Temperature (° C.) 400 400 H2 produced/mole of glycerol feed 1.01 0.83 %Carbon/Carbon in Feed CO₂ 42.8% 41.7% CH₄ 15.7% 16.1% C₂H₆ 15.8% 11.9%C₃H₈ 19.9% 18.2% C₄H₁₀ 1.8% 3.0% C₅H₁₂ 2.3% 3.4% C₆H₁₄ 1.0% 1.7% C₆ ⁺Hydrocarbons in Organic Phase 0.0% 1.1% C₂-C₆ Oxygenates in OrganicPhase 0.0% 0.7% C₂-C₆ Oxygenates in Aqueous Phase 0.2% 0.1%

Example 36

A bimetallic catalyst system containing platinum and rhenium (5 wt %platinum with a molar ratio of Pt:Re of 1:5) supported on activatedcarbon (Calgon UU 60×120 mesh carbon) was prepared using an incipientwetness technique. Activated carbon was added slowly to a 30% hydrogenperoxide solution. After addition of the carbon was completed, themixture was left overnight. The aqueous phase was decanted and thecarbon was washed three times with deionized water, and then dried undervacuum at 100° C. An aqueous solution, with a volume equal to theincipient wetness volume for the carbon to be impregnated and containingdihydrogen hexachloroplatinate (IV) hexahydrate (Alfa Aesar, 39.85% Pt)and perrhemic acid solution (Alfa Aesar, 76.41% HReO₄) was applied dropwise, while stirring, to hydrogen peroxide functionalized carbon. Thewetted carbon was then dried at 100° C. under vacuum.

Example 37

11.97 grams of the 1:5 Pt/Re catalyst described in Example 36 wereloaded into the 8.5 mm diameter stainless steel tube as described inExample 4 and the reactor system illustrated in Example 1. The catalystwas reduced with flowing hydrogen at 350° C. for two hours before liquidfeed was introduced to the catalyst bed. A 57.2 wt % sorbitol solutioncontaining 0 ppm sulfate in water solution was fed downflow across thereactor at a WHSV of 1.20 grams of sorbitol per gram of catalyst perhour. The block heaters were controlled such that the first 10.1 cm ofthe reactor was held at 260° C., the second 10.1 cm of the reactor wasat 260° C., the next 10.1 cm of the reactor was at 360° C., and the last10.1 cm of the reactor at 410° C. The separator pressure was maintainedat 600 psig. The effluent from the reactor was cooled down with a watercooled condenser and separated in a three-phase separator. The productfractions were analyzed as described in Example 5. In addition, theorganic phase was collected, separated, and weighed, with a sample sentto Southwest Research Institute (San Antonia, Tex.) for gasolineanalysis. In this system, there was complete conversion of the glycerol.Table 11 below shows the yields of hydrogen as well as the yields ofcarbon containing product compounds.

TABLE 11 Yields of Hydrogen and Carbon Containing Products from Example37 Block 1 Temperature (° C.) (FIG. 8, 10a) 260 Block 2 Temperature (°C.) (FIG. 8, 10b) 260 Block 3 Temperature (° C.) (FIG. 8, 10c) 360 Block4 Temperature (° C.) (FIG. 8, 10d) 410 Products moles of H2/mole ofSorbitol feed 1.36 % Carbon/Carbon in Feed CO2 44.37 Methane 9.24 Ethane8.25 Propane 11.74 Butane 6.53 Pentane 5.66 Hexane 3.79 C7-C13 Normal0.08 C4-C13 Isoparaffin 0.99 C6-C12 Aromatic 2.45 C8-C11Naphthalene/Napthenes 0.93 C5-C10 Olefins 0.45 C4-C6 OxygenatedCompounds in 1.68 Organic Phase Oxygenates in Aqueous Phase 3.83

Conversion of Oxygenates to C5+ Compounds Using Acidic Catalysts Example38

An aqueous 1.0 molar lanthanum nitrate solution was prepared and addedto H-mordenite extrudates (BASF 712A-5-2641-1) for a target of 3 weight% La on the catalyst after the subsequent decomposition of the metalprecursor. The La solution was mixed briefly with the catalyst and thensoaked at 80° C. for 6 hours. The excess liquid was then removed and thecatalyst rinsed with deionized water. The catalyst was then dried in avacuum oven and calcined in air at 55° C. Following this, the catalystwas ground and sieved to restrict the particles sizes to those that weremaintained on a 60 mesh screen after passing through an 18 mesh screen.

Example 39

Deionized water was added to H-mordenite extrudates (BASF 712A-5-2641-1,with particle sizes restricted to those that were maintained on a 60mesh screen after passing through an 18 mesh screen) until extra watercovered the support. An aqueous 0.36 molar nickel nitrate solution wasthen added to the wet support to target 1 weight % Ni afterdecomposition of the metal precursor. The catalyst was mixed briefly andleft to soak for 48 hours. The catalyst was then dried in a vacuum ovenand calcined in air at 400° C.

Example 40

An aqueous 1.0 molar europium chloride solution was prepared and addedto H-Mordenite (BASF 712A-5-2641-1, with particle sizes restricted tothose that were maintained on a 60 mesh screen after passing through an18 mesh screen) for a target of 3 weight % Eu on the catalyst after thesubsequent decomposition of the metal precursors. The Eu solution wasmixed briefly with the catalyst and then soaked at 80° C. for 6 hours.The excess liquid was then removed and the catalyst rinsed withdeionized water. The catalyst was then dried in a vacuum oven andcalcined in air at 550° C. Following this the catalyst was ground andsieved to restrict the particles sizes to those that were maintained ona 60 mesh screen after passing through an 18 mesh screen.

Example 41

H-Beta zeolite extrudates (1.6 mm diameter extrudates) were ground andsieved to restrict the particle sizes to those that were maintained on a60 mesh screen after passing through an 18 mesh screen. An aqueousgallium nitrate solution was added by incipient wetness to target 1.2weight % Ga on the catalyst after decomposition of the metal precursor.The catalyst was then dried in a vacuum oven and calcined in air at 400°C.

Example 42

Phosphoric acid was diluted with deionized water and added by incipientwetness to a Davicat SiO₂/Al₂O₃ support (Grace-Davis, with particlesizes restricted to those that were maintained on a 60 mesh screen afterpassing through an 18 mesh screen) to target 5 weight % phosphorous onthe catalyst. The catalyst was then dried in a vacuum oven overnight andsubsequently calcined in a stream of flowing air at 500° C.

Example 43

An aqueous nickel nitrate solution was added to an alumina bound ZSM-5zeolite preparation (SiO₂:Al₂O₃ 30:1, with particle sizes restricted tothose that were maintained on a 60 mesh screen after passing through an18 mesh screen) using an incipient wetness technique to target a nickelloading of 1.0 weight %. The preparation was dried overnight in a vacuumoven and subsequently calcined in a stream of flowing air at 400° C.

Example 44

An aqueous gallium nitrate solution was added to an alumina bound ZSM-5zeolite preparation (SiO₂:Al₂O₃ 80:1, with particle sizes restricted tothose that were maintained on a 60 mesh screen after passing through an18 mesh screen) using an incipient wetness technique to target a galliumloading of 1.2 weight %. The preparation was dried overnight in a vacuumoven and subsequently calcined in a stream of flowing air at 400° C.

Example 45

Catalyst systems produced using the methods of Examples 38 to 44 wereinvestigated for the vapor-phase condensation of various oxygenates at atemperature from 325° C. to 375° C. and a total pressure between 200psig and 625 psig, and with WHSVs ranging from 1.9 to 42.8. In theseinvestigations, two different size reactors were used; 15 and 18milliliters of catalyst were loaded into a 8.5 mm internal diameterstainless steel tube reactor or between 50 and 70 milliliters ofcatalyst were loaded into a 21.2 mm stainless steel tube reactor(Example 4). The reaction process flow was as described in Example 1 orExample 3 depending on the feedstock, with an analysis completed asdescribed in Example 5.

Operating conditions and results from these experiments are shown inTable 12. Where feed compositions add up to less than 100%, the balancewas water. As these results show, a variety of oxygenates, includingalcohols and ketones, both 3 carbon and 5 carbon, are substrates whichmay be converted to C₅+ hydrocarbons across a broad range of conditions.Zeolites are particularly useful in these conversions, as shown byexperiments FF, GG, HH, II, JJ, LL, and MM. Experiments FF, GG, HH, II,and JJ show that the main products of alcohol conversion acrossmordenite and beta zeolites were olefinic condensation products. Thephosphorous impregnated silica alumina catalyst, experiment KK,demonstrated a similar product selectivity profile. In contrast, theZSM-5 based catalysts, Experiments LL and MM, produced significantfractions of aromatic and paraffinic components.

TABLE 12 Vapor Phase Condensation of Oxygenates Over Acid Catalysts 5%Ni/ Phosphorous/ 30:1 Ga/80:1 La/ Ni/ Eu/ Eu/ Ga/ Silica- SiO₂:Al₂O₃SiO₂:Al₂O₃ Catalyst mordenite mordenite mordenite mordenite Beta AluminaZSM-5 ZSM-5 Experiment FF GG HH II JJ KK LL MM Feed Feed J Feed K Feed LFeed K Feed K Feed M Feed K Feed N WHSV wt_(feed)/ 1.9 2.1 2.2 1.9 3.12.7 42.8 2.1 (wt_(cat) hr) Reactor ° C. 325 350 325 375 375 375 375 375Temperature Pressure psig 625 625 600 600 600 600 200 625 Reactor OutletYield Distribution C⁴⁻ Alkanes wt % of 2.9 0.7 3.9 3.6 1.2 1.6 9.6 7.0feed carbon C⁴⁻ Olefins wt % of 19.5 47.7 11.3 32.9 32.5 73.5 10.8 0.5feed carbon Total C⁴⁻ wt % of 22.3 48.4 15.3 36.5 33.7 75.1 20.5 7.5Hydrocarbons feed carbon C₅₊ wt % of 6.6 0.8 16.9 3.1 4.3 1.9 29.6 8.5Paraffins feed carbon C₅₊ Olefins wt % of 56.2 46.9 43.1 56.6 52.0 18.421.7 0.1 feed carbon Naphthenes wt % of 0.0 2.5 1.5 5.6 3.2 3.4 2.7 1.0feed carbon Aromatics wt % of 0.0 0.0 1.4 0.0 2.0 0.0 18.0 79.1 feedcarbon Other C₅₊ wt % of 0.8 0.1 5.7 1.5 0.2 0.0 7.1 0.0 Hydrocarbonsfeed carbon Total C₅₊ wt % of 63.6 50.3 68.6 66.7 61.8 23.7 79.2 88.6Hydrocarbons feed carbon Feed J - 50% 2-pentanol Feed K - 50% isopropylalcohol Feed L - 59% 2-pentanol Feed M - 90% isopropyl alcohol Feed N -89.6% Acetone

Production of C5+ Compounds from Oxygenated Hydrocarbons Example 46

A catalyst preparation technique identical to that of Example 44 wasfollowed with the exception that the alumina bound ZSM-5 material had aSiO₂:Al₂O₃ ratio of 30:1.

Example 47

A catalyst produced using the method of Example 46 was investigated forthe vapor-phase condensation of a mixture of oxygenates at 375° C. and200 psig. In this investigation, 11.3 grams of catalyst were loaded intoa 8.5 mm internal diameter stainless steel tube reactor as described inExample 4. The reaction process flow was as described in Example 3. Theoxygenate mix included, by weight, 25% 2-pentanone, 20% 3-pentanone, 20%2-pentanol, 10% isopropyl alcohol, 10% valeric acid, 5% 2-methyltetrahydrofuran. This mixture was added using one pump in the Example 3reactor system while the second pump added water so that the totalcombined feed contained 60 weight % water and 40 weight % of mixedoxygenates.

The process was monitored for a period of 128 hours, with samplesperiodically removed from the system to analyze the process performance.Each analysis was completed as described in Example 5. FIG. 15 shows thefraction of feed carbon that exited the reactor system as C₅₊ compoundsas a function of time. FIG. 16 shows the fraction of feed carbon thatexited the reactor system as an aromatic hydrocarbon as a function oftime. FIG. 14 shows the fraction of feed carbon that exited the reactorsystem as oxygenates as a function of time.

As FIGS. 14, 15 and 16 show, the catalyst system is able to operate forextended periods of time with an oxygenate mix that contains a mixtureof oxygenates, including alcohols, ketones, an acid, and atetrahydrofuran. Over time the production of C₅+ compounds remainsrelatively stable, while the amount of aromatic hydrocarbons present inthe product drops and the breakthrough of oxygenated compounds increases(FIG. 14). It is believed that the catalyst deactivation is primarilydue to the accumulation of carbonaceous deposits limiting theaccessibility of the reactants to the active sites.

Example 48

An aqueous solution of hexachloroplatinic acid and perrhenic acid wasadded to a carbon catalyst support (OLC-AW, Calgon, with particle sizesrestricted to those that were maintained on a 50 mesh screen afterpassing through an 120 mesh screen) using an incipient wetness techniqueto target a platinum loading of 1.8% and a rhenium loading of 6.3% onthe catalyst after subsequent decomposition of the metal precursors. Thepreparation was dried overnight in a vacuum oven and subsequentlyreduced in a stream of flowing hydrogen at 400° C. After being reducedthe catalyst was stored in a nitrogen atmosphere until ready for use.

Example 49

A catalyst preparation technique identical to that of Example 44 wasfollowed with the exception that the alumina bound ZSM-5 material had aSiO₂:Al₂O₃ ratio of 150:1.

Example 50

Hexachloroplatinic acid and perrhenic acid dissolved in water were addedto a monoclinic zirconia catalyst support (N or Pro Saint Gobain,product code SZ31164, with particle sizes restricted to those that weremaintained on a 60 mesh screen after passing through an 18 mesh screen)using an incipient wetness technique to target a platinum loading of1.8% and a rhenium loading of 6.3% on the catalyst after subsequentdecomposition of the metal precursors. The preparation was driedovernight in a vacuum oven and subsequently calcined in a stream offlowing air at 400° C.

Example 51

The same procedure used for preparing the catalyst of Example 50 wasfollowed with the exception that the target rhenium loading was 1.8%.

Example 52

An 80:1 SiO₂:Al₂O₃ ratio ZSM-5 zeolite (Zeolyst International, CBV 8014)was mixed with a 1:1 molar ratio of ZnO and Al₂O₃ powders so that theZnO and Al₂O₃ (Dispal 18N4-80, Sasol North America, Houston, Tex.)combined comprised 30 weight % of the total solids. Dilute nitric acidwas added at a level of 2 weight % HNO₃ to the combined ZnO and Al₂O₃.The dough consistency was adjusted with water addition to form aworkable dough suitable for extrusion and the mixture was extruded usinga laboratory scale extruder. The extrudates were dried overnight undervacuum at 100° C. and subsequently calcined at 600° C. under flowingair.

Example 53

An aqueous solution of gallium nitrate was added to the material ofExample 52, with particle sizes restricted to those that were maintainedon a 60 mesh screen after passing through an 18 mesh screen, using anincipient wetness technique to target a gallium loading of 1.2 weight %.The preparation was dried overnight in a vacuum oven and subsequentlycalcined in a stream of flowing hydrogen at 400° C.

Example 54

An aqueous solution of nickel nitrate was added to the material ofExample 52, with particle sizes restricted to those that were maintainedon a 60 mesh screen after passing through an 18 mesh screen, using anincipient wetness technique to target a nickel loading of 1.0 weight %.The preparation was dried overnight in a vacuum oven and subsequentlycalcined in a stream of flowing hydrogen at 400° C.

Example 55

The catalyst systems referenced in Examples 6, 46, 48, 49, 51, 53, and54 were investigated for the conversion of glycerol, sorbitol, sucrose,and xylose to hydrocarbons using the reactor configuration described inExample 2. The studies were conducted using two 21.2 mm internaldiameter stainless steel tube reactors shown in Example 4, with ananalysis completed as described in Example 5. Tungstated zirconia (N orPro-Saint Gobain, product code SZ61143, with particle sizes restrictedto those that were maintained on a 60 mesh screen after passing throughan 18 mesh screen) was placed on top of the condensation catalystinstalled in the second reactor to provide for a zone for vaporizationof the first reactor effluent prior to entering the condensationcatalyst.

Table 13 shows the results of these investigations. For Experiment NN(38% Sucrose+7% Xylose), a stream of hydrogen with a targeted flow rateequal to 3 times the moles of sucrose plus 1.5 times the moles of xylosewas combined with the feed prior to entering the reactor. The otherexperiments were conducted without externally supplied hydrogen. Heatersexternal to the reactor, shown in FIG. 9 as 10 a, 10 b, 10 c, 10 d, 23a, 23 b, 23 c, and 23 d, were used to maintain the reactor walltemperatures, as indicated in Table 13. The hydrocarbon products ofthese studies, disclosed in Table 13, were grouped into a C⁴⁻ fraction,which are predominately present in the gas phase at ambient temperatureand pressure, and a C₅₊ fraction, which are generally suitable forincorporation into liquid fuels. The results show that a variety ofsugars and polyhydric alcohols may be readily converted to C₅₊hydrocarbons by the processes described here. The products containedmainly paraffin and aromatic constituents. The breakdown of paraffinsand aromatics within this

TABLE 13 Conversion of Sugars and Polyhydric Alcohols to C5+Hydrocarbons Experiment NN OO PP QQ Catalyst Descriptions HydrogenationExample 6 None None None APR/Deoxygenation Example 48 Example 51 Example51 Example 50 Condensation Example 49 Example 53 Example 46 Example 54Catalyst Loadings Hydrogenation grams 10 — — — APR/Deoxygenation grams40 52 60 60 Tungstated Zirconia grams 71 60 ~60 58 Condensation grams 6260 60 60 Heater Block Temperature Ranges, Inlet of Catalyst Bed-Outletof Catalyst Bed Hydrogenation ° C. 100-150 — — — APR/Deoxygenation ° C.245-265 250-270 335-365 275-285 Tungstated Zirconia ° C. 250-375 370-370395-375 395-375 Condensation ° C. 375-375 385-385 375-375 375-375Pressures First Reactor Outlet psig 625 625 625 625 2nd Reactor Outletpsig 625 350 250 350 Feed Feed O Feed P Feed P Feed Q Hydrogenproduction mol/mol feed −2.85 0.73 0.57 0.50 WHSV wt_(feed)/(wt_(cat)hr) 1.6 1.9 2.0 2.0 Reactor Outlet Yield Distribution C⁴⁻ Alkanes wt %of feed carbon 21.2 26.9 8.1 13.0 C⁴⁻ Olefins wt % of feed carbon 1.11.4 1.3 5.2 Total C⁴⁻ Hydrocarbons wt % of feed carbon 22.3 28.3 9.418.1 C₅₊ Paraffins wt % of feed carbon 20.0 7.9 9.5 11.3 C₅₊ Olefins wt% of feed carbon 0.8 1.9 1.2 7.8 Naphthenes wt % of feed carbon 1.9 1.41.6 1.2 Aromatics wt % of feed carbon 25.0 17.8 48.4 22.3 Other C₅₊Hydrocarbons wt % of feed carbon 0.0 1.1 0.2 3.4 Total C₅₊ Hydrocarbonswt % of feed carbon 47.7 30.1 61.0 46.1 Feed O - 38% Sucrose, 7% XyloseFeed P - 50% Glycerol Feed Q - 50% Sorbitol

Example 56

The process described in Example 55 and exemplified by Experiment QQ inTable 13 was operated for a period of more than 400 hours. After aninitial period of time in operation, the conversion to aromaticcomponents and the yield of hydrocarbons dropped, shown in FIGS. 18 and19 as Cycle 1. In FIG. 18, the heating value of C₅₊ hydrocarbons presentat the outlet of the second reactor, as a percentage of the heatingvalue of the feed, is shown. In FIG. 19, the carbon present as aromatichydrocarbons at the outlet of the second reactor is shown as apercentage of the carbon present in the feed. After approximately 120hours on stream, the second reactor was bypassed while the first reactorcontinued operating. An oxidative regeneration of the catalyst in thesecond reactor was then performed. During the regeneration, a flow ofnitrogen and air was initiated so that the target oxygen concentrationat the second reactor inlet was 1 mol %. The second reactor blocktemperatures were then raised to 500° C. and the flow of nitrogen andoxygen continued until carbon dioxide was no longer detected at thesecond reactor outlet. The oxygen concentration was then raised to atarget level of 5 mol %. This flow was continued until carbon dioxidewas no longer detected at the second reactor outlet. At this time theoxygen flow was discontinued while the nitrogen flow continued. Thesecond reactor block temperatures were then reduced to 400° C. while thecomposition of the gas flowing through the catalyst bed was changed tohydrogen. The second reactor block temperatures were then adjusted tothose shown for Experiment QQ in Table 13. The second reactor was thenplaced back on line, targeting the conditions shown for Experiment QQ inTable 13. The second reactor was then subjected to multiple cycles ofoperation and regeneration, with the results for the period of time inoperation shown in FIGS. 18 and 19. As these results show, theregeneration of the condensation catalyst resulted in a restoration ofactivity, consistent with the theory that deposition of carbonaceousmaterials were the main cause of a drop in catalyst performance overtime. Furthermore, the results show that the condensation catalyst maybe regenerated multiple times without a significant loss of performance.

Preparation of Gasoline Compositions Example 57

A gasoline composition (gasoline composition GC1) was prepared byadmixing a base gasoline with 5% vol., based on the volume of the finalgasoline composition, of the product of the process described in Example55 and exemplified by Experiment PP in Table 13.

The base gasoline used and the gasoline composition prepared aredetailed in Table 14.

Example 58

A gasoline composition (gasoline composition GC2) was prepared byadmixing a base gasoline with 10% vol., based on the volume of the finalgasoline composition, of the product of the process described in Example55 and exemplified by Experiment OO in Table 13.

The base gasoline used and the gasoline composition prepared aredetailed in Table 14.

TABLE 14 Property Unit Base Gasoline GC1 GC2 RVP kPa 92.9 88.7 85.8Density Kg/m³ 727.5 735.2 736.6 IBP ° C. 26.9 27.6 27.6 FBP ° C. 194.3206.8 198.2 Residue % v 1 1.2 1.1 Recovery % v 95.9 95.8 958 Loss % v3.1 3 3.1 T10 ° C. 39.9 40.2 41.2 T20 ° C. 51 51.5 52.8 T30 ° C. 63.464.3 65.9 T40 ° C. 76.4 78.4 79.8 T50 ° C. 89.9 92.5 94.2 T60 ° C. 102.6106 107.4 T70 ° C. 114.8 118.8 120.1 T80 ° C. 129 134 136.1 T90 ° C. 149154.1 155.6 T95 ° C. 165 170.4 171 E70 % v 35.1 34.1 32.9 E100 % v 57.955.3 54 E120 % v 74 70.7 69.8 E150 % v 90 88 87 E180 % v 97.5 96.6 96.7RON 95.6 96.4 96.3 MON 85.4 85.5 85.1

It can be seen from the information presented in Table 14 above that thegasoline compositions comprising the products prepared by the processdescribed in Example 55 have very similar distillation characteristicsto the base gasoline, and advantageously have a higher Road OctaneNumber (RON) than the base gasoline. It can also be seen from theinformation presented in Table 14 above that the gasoline compositionscomprising the products prepared by the process described in Example 55have a lower Reid Vapour Pressure (RVP) compared to the base gasoline,which may advantageously be used to decrease the RVP of a gasoline inorder to meet specific requirements of the gasoline composition, oralternatively allow the addition of greater amounts of gasolinecomponents whose addition to gasoline compositions may have been limiteddue to the volatility of such components.

Example 59

Two separate gasoline compositions were prepared using sorbitol andsucrose as a feedstock, and then analyzed for their carbon 14 (14C)concentration as compared to petroleum-based gasoline.

The first gasoline sample (V-18510) was produced from a 50% solution ofsorbitol in water using a reactor system similar to that described inExample 55, except that the system included a second condensationreactor in a lead/lag configuration. The APR/deoxygenation catalyst wasprepared as described in Example 50, while the condensation catalyst wasprepared as described in Example 43. Multiple runs using the sorbitolfeedstock where conducted over various temperatures and conditions.APR/deoxygenation reactions were conducted in a single reactor over alow to high temperature profile with temperatures varied from 110° C. to130° C. at the inlet and from 235° C. to 250° C. at the outlet.Condensation reactions were conducted in a two reactor system with thetemperature in the lead reactor varied from 345° C. to 385° C. and thelag reactor varied from 260° C. to 385° C. Pressure conditions were alsovaried from 620 psig to 630 psig for the APR/deoxygenation reactions and95 psig to 105 psig for the condensation reactions. WHSV was varied from0.9 to 1.1 hr−1 for the APR/deoxygenation catalyst.

A second gasoline sample (V-18512) was prepared from a collective sampleof gasoline produced from sucrose using a reactor system as illustratedin FIG. 6. Sucrose was fed at various temperatures, pressures and WHSVover a hydrogenation catalyst containing 2.5% ruthenium on UU carbon(Calgon, with particle sizes restricted to those that were maintained ona 120 mesh screen after passing through a 60 mesh screen), and theAPR/deoxygenation catalyst and condensation catalyst described above forthe sorbitol feed. Conditions for the hydrogenation reaction varied withtemperatures in the range of 115° C. to 140° C., and pressures in therange of 620 psig to 680 psig. The WHSV, temperature and pressureconditions for the APR/deoxygenation were as described for sorbitol. Thecondensation reaction was conducted in a single condensation reactorwith the WHSV, temperature and pressure conditions the same as thatdescribed above for the lead reactor.

The product streams from the various runs of sorbitol were combined intoa single sample (V-18510) and then subjected to a distillation step asdescribed in Example 29. The product streams from the various runs ofsucrose were also combined into a single sample (V-18512) and thensubjected to distillation as described in Example 29. Distillationfractions having a boiling point of less than 210° C. were collected forfurther blending into final fuel compositions. A sample of each fractionwas also collected for 14C testing.

Carbon 14 testing was performed by Beta Analytical Inc (Miami, Fla. USA)using ASTM-D6866, Test Methods for Determining the Biobased Content ofNatural Range Materials Using Radiocarbon and Isotope Ratio MassSpectrometry Analysis. In addition to 14C testing on samples V-18510 andV-18512, a biobased determination was also performed on two additionalsamples collected from separate retail gas stations in Madison, Wis. Thefirst sample (V-RRGWE) was a regular unleaded gasoline identified ascontaining up to 10% ethanol, while the second sample (V-SVPNE) waspremium gasoline. The results of the study are listed in Table 15 below.

Mean Percentage of Sample No. ASTM-D6866 Method Biobased MaterialV-18510 Method - B 99% V-18512 Method - B 99% V-RRGWE Method - B  7%V-SVPNE Method - B  2%

1-15. (canceled)
 16. A light fuel component comprising one or more C₄₊compounds derived from a water-soluble oxygenated hydrocarbon, the lightfuel component having a component final boiling point in the range offrom 150 to 220° C., a component density at 15° C. in the range of from700 to 890 kg/m³, a component sulfur content of at most 5 mg/kg, acomponent oxygen content of at most 3.5% wt., a component RON in therange of from 80 to 110, and a component MON in the range of from 70 to100.
 17. The light fuel component of claim 16 wherein at least afraction of the C₄₊ compounds derived from a water-soluble oxygenatedhydrocarbon are less than 100 years old, as calculated from the carbon14 concentration of the fuel component.
 18. The light fuel component ofclaim 16 wherein the one or more C₄₊ compounds comprise primarilycompounds having from about 4 to about 9 carbon atoms.
 19. A gasolinecomposition comprising: a light fuel component comprising one or moreC₄₊ compounds derived from a water-soluble oxygenated hydrocarbon, thelight fuel component having a component final boiling point in the rangeof from 150 to 220° C., a component density at 15° C. in the range offrom 700 to 890 kg/m³, a component sulfur content of at most 5 mg/kg, acomponent oxygen content of at most 3.5% wt., a component RON in therange of from 80 to 110, and a component MON in the range of from 70 to100; wherein the gasoline composition has an initial boiling point inthe range of from 15° C. to 70° C. (IP123), a final boiling point of atmost 220° C. (1P123), a RON in the range of from 85 to 110 (ASTM D2699)and a MON in the range of from 75 to 100 (ASTM D2700).
 20. The gasolinecomposition of claim 18 wherein at least a fraction of the C₄₊ compoundsderived from a water-soluble oxygenated hydrocarbon are less than 100years old, as calculated from the carbon 14 concentration of the fuelcomponent.
 21. The gasoline composition of claim 16 wherein the one ormore C₄₊ compounds comprise primarily compounds having from about 4 toabout 9 carbon atoms.
 22. An aviation gasoline composition comprising: alight fuel component comprising one or more C₄₊ compounds derived from awater-soluble oxygenated hydrocarbon, the light fuel component having acomponent final boiling point in the range of from 150 to 220° C., acomponent density at 15° C. in the range of from 700 to 890 kg/m³, acomponent sulfur content of at most 5 mg/kg, a component oxygen contentof at most 3.5% wt., a component RON in the range of from 80 to 110, anda component MON in the range of from 70 to 100; the aviation gasolinecomprising a Reid Vapor Pressure at 37.8° C. in the range of from 38.0to 49.0 kPa (ASTM D323), a final boiling point of at most 1870° C.(IP123), a Lean Mixture Motor Octane Number of 80 or more, a RichMixture Octane Number of 87 or more, and a tetraethyl lead content of atmost 0.85 gPb/1.
 23. The aviation gasoline composition of claim 20wherein at least a fraction of the C₄₊ compounds derived from awater-soluble oxygenated hydrocarbon are less than 100 years old, ascalculated from the carbon 14 concentration of the fuel component. 24.The aviation gasoline of claim 22 wherein the one or more C₄₊ compoundscomprise primarily compounds having from about 4 to about 9 carbon atoms25. A moderate fuel component comprising one or more C₄₊ compoundsderived from a water-soluble oxygenated hydrocarbon, the moderate fuelcomponent having a component initial boiling point in the range of from120 to 215° C., a component final boiling point in the range of from 220to 320° C., a component density at 15° C. in the range of from 700 to890 kg/m³, a component sulfur content of at most 0.1% wt., a componenttotal aromatics content of at most 30% vol, a component freeze point of−40° C. or lower, a component smoke point of at least 18 mm, a componentviscosity at −20° C. in the range of from 1 to 10 cSt, and a componentspecific energy content in the range of from 40 to 47 MJ/kg.
 26. Themoderate fuel component of claim 25 wherein at least a fraction of theC₄₊ compounds derived from a water-soluble oxygenated hydrocarbon areless than 100 years old, as calculated from the carbon 14 concentrationof the fuel component.
 27. The moderate fuel component of claim 25wherein the one or more C₄₊ compounds comprising primarily compoundshaving from about 7 to about 14 carbon atoms.
 28. A kerosene compositioncomprising: a moderate fuel component comprising one or more C₄₊compounds derived from a water-soluble oxygenated hydrocarbon, themoderate fuel component having a component initial boiling point in therange of from 120 to 215° C., a component final boiling point in therange of from 220 to 320° C., a component density at 15° C. in the rangeof from 700 to 890 kg/m³, a component sulfur content of at most 0.1%wt., a component total aromatics content of at most 30% vol., acomponent freeze point of −40° C. or lower, a component smoke point ofat least 18 mm, a component viscosity at −20° C. in the range of from 1to 10 cSt, and a component specific energy content in the range of from40 to 47 MJ/kg; wherein the kerosene composition has an initial boilingpoint in the range of from 80 to 150° C., a final boiling point in therange of from 200 to 320° C. and a viscosity at −20° C. in the range offrom 0.8 to 10 mm²/s (ASTM D445).
 29. The kerosene composition of claim28 wherein at least a fraction of the C₄₊ compounds derived from awater-soluble oxygenated hydrocarbon are less than 100 years old, ascalculated from the carbon 14 concentration of the fuel component. 30.The kerosene composition of claim 28 wherein the one or more C₄₊compounds comprising primarily compounds having from about 7 to about 14carbon atoms
 31. A heavy fuel component comprising one or more C₄₊compounds derived from a water-soluble oxygenated hydrocarbon, the heavyfuel component having a component T95 in the range of from 220 to 380°C., a component flash point in the range of from 30 to 70° C., acomponent density at 15° C. in the range of from 700 to 900 kg/m³, acomponent sulphur content of at most 5 mg/kg, a component oxygen contentof at most 10% wt., and a component viscosity at 40° C. in the range offrom 0.5 to 6 cSt.
 32. The heavy fuel component of claim 31 wherein atleast a fraction of the C₄₊ compounds derived from a water-solubleoxygenated hydrocarbon are less than 100 years old, as calculated fromthe carbon 14 concentration of the fuel component.
 33. The heavy fuelcomponent of claim 31 wherein the one or more C₄₊ compounds comprisingprimarily compounds having from about 12 to about 24 carbon atoms
 34. Adiesel fuel composition comprising: a heavy fuel component comprisingone or more C₄₊ compounds derived from a water-soluble oxygenatedhydrocarbon, the heavy fuel component having a component T95 in therange of from 220 to 380° C., a component flash point in the range offrom 30 to 70° C., a component density at 15° C. in the range of from700 to 900 kg/m³, a component sulfur content of at most 5 mg/kg, acomponent oxygen content of at most 10% wt., and a component viscosityat 40° C. in the range of from 0.5 to 6 cSt; wherein the diesel fuelcomposition has an initial boiling point in the range of from 130° C. to230° C. (IP123), a final boiling point of at most 410° C. (IP123) and acetane number in the range of from 35 to 120 (ASTM D613).
 35. The dieselfuel composition of claim 34 wherein at least a fraction of the C₄₊compounds derived from a water-soluble oxygenated hydrocarbon are lessthan 100 years old, as calculated from the carbon 14 concentration ofthe fuel component.
 36. The diesel fuel composition of claim 34 whereinthe one or more C₄₊ compounds comprising primarily compounds having fromabout 12 to about 24 carbon atoms.